WorldWideScience

Sample records for solvated electrons produced

  1. Continuous registration of optical absorption spectra of periodically produced solvated electrons

    International Nuclear Information System (INIS)

    Krebs, P.

    1975-01-01

    Absorption spectra of unstable intermediates, such as solvated electrons, were usually taken point by point, recording the time-dependent light absorption after their production by a flash. The experimental arrangement for continuous recording of the spectra consists of a conventional one beam spectral photometer with a stabilized white light source, a monochromator, and a light detector. By periodic production of light absorbing intermediates such as solvated electrons, e.g., by ac uv light, a small ac signal is modulated on the light detector output which after amplification can be continuously recorded as a function of wavelength. This method allows the detection of absorption spectra when disturbances from the outside provide a signal-to-noise ratio smaller than 1

  2. Electron spin resonance of the solvation of radiation-produced silver atoms in alcohol-water mixtures

    International Nuclear Information System (INIS)

    Li, A.S.W.; Kevan, L.

    1982-01-01

    Frozen solutions of silver salts exposed to 60 Co γ-irradiation form silver atoms by reaction of radiation-produced electrons with the silver ion. At 4 K the silver atoms are initially produced in a nonequilibrium or presolvated state and upon brief thermal excitation to 77 K the first solvation shell geometry changes towards an equilibrium or solvated silver atom. This is most pronounced in water but also occurs in methanol, ethanol and n-propanol matrices. The changes in the electron spin resonance magnetic parameters upon silver atom solvation have been determined. In alcohol-water mixtures Ag 0 is preferentially solvated by polycrystalline water at low alcohol concentration. Above a particular alcohol mole percent Ag 0 suddenly changes its environment to a glassy alcohol one. This sudden change occurs at 17, 13 and 6 mol % methanol, ethanol and n-propanol, respectively. These mole percents correlate with the minimum of the excess enthalpy of mixing and with the hydrogen atom trapping ability of these alcohol-water mixtures. The results also suggest that the local environmental disorder around Ag 0 increases with alcohol chain length in alcohol-water frozen solutions. (author)

  3. Theories of the solvated electron

    International Nuclear Information System (INIS)

    Kestner, N.R.

    1987-01-01

    In this chapter the authors address only the final state of the electron, that is, the solvated state, which, if no chemical reaction would occur, is a stable entity with well-defined characteristics. Except for some metal-ammonia solutions, and possible a few other cases, such stable species, in reality, exist but a short time (often as short as microseconds). Nevertheless, this chapter only deals with this final time-independent,'' completely solvated,'' equilibrium species. The last statement is added to indicate that the solvent around the electron has also come to thermal equilibrium with the field of the charge

  4. Solvated electron structure in glassy matrices

    International Nuclear Information System (INIS)

    Kevan, L.

    1981-01-01

    Current knowledge of the detailed geometrical structure of solvated electrons in aqueous and organic media is summarized. The geometry of solvated electrons in glassy methanol, ethanol, and 2-methyltetrahydrofuran is discussed. Advanced electron magnetic resonance methods and development of new methods of analysis of electron spin echo modulation patterns, second moment line shapes, and forbidden photon spin-flip transitions for paramagnetic species in these disordered systems are discussed. 66 references are cited

  5. Relaxation dynamics following transition of solvated electrons

    International Nuclear Information System (INIS)

    Barnett, R.B.; Landman, U.; Nitzan, A.

    1989-01-01

    Relaxation dynamics following an electronic transition of an excess solvated electron in clusters and in bulk water is studied using an adiabatic simulation method. In this method the solvent evolves classically and the electron is constrained to a specified state. The coupling between the solvent and the excess electron is evaluated via the quantum expectation value of the electron--water molecule interaction potential. The relaxation following excitation (or deexcitation) is characterized by two time scales: (i) a very fast (/similar to/20--30 fs) one associated with molecular rotations in the first solvation shell about the electron, and (ii) a slower stage (/similar to/200 fs), which is of the order of the longitudinal dielectric relaxation time. The fast relaxation stage exhibits an isotope effect. The spectroscopical consequences of the relaxation dynamics are discussed

  6. Theory of optical spectra of solvated electrons

    International Nuclear Information System (INIS)

    Kestner, N.R.

    1975-01-01

    During the last few years better theoretical models of solvated electron have been developed. These models allow one to calculate a priori the observable properties of the trapped electron. One of the most important and most widely determined properties is the optical spectrum. In this paper we consider the predictions of the theories not only as to the band maximum but line shape and width. In addition we will review how the theories predict these will depend on the solvent, pressure, temperature, and solvent density. In all cases extensive comparisons will be made with experimental work. In addition four new areas will be explored and recent results will be presented. These concern electrons in dense polar gases, the time development of the solvated electron spectrum, solvated electrons in mixed solvents, and photoelectron emission spectra (PEE) as it relates to higher excited states. This paper will review all recent theoretical calculations and present a critical review of the present status and future developments which are anticipated. The best theories are quite successful in predicting trends, and qualitative agreement concerning band maximum. The theory is still weak in predicting line shape and line width

  7. Ultrafast transient-absorption of the solvated electron in water

    International Nuclear Information System (INIS)

    Kimura, Y.; Alfano, J.C.; Walhout, P.K.; Barbara, P.F.

    1994-01-01

    Ultrafast near infrared (NIR)-pump/variable wavelength probe transient-absorption spectroscopy has been performed on the aqueous solvated electron. The photodynamics of the solvated electron excited to its p-state are qualitatively similar to previous measurements of the dynamics of photoinjected electrons at high energy. This result confirms the previous interpretation of photoinjected electron dynamics as having a rate-limiting bottleneck at low energies presumably involving the p-state

  8. Silver atom solvation and desolvation in ice matrices: study of solvation shell geometry by electron spin resonance and electron spin echo methods

    Energy Technology Data Exchange (ETDEWEB)

    Kevan, L; Narayana, P A

    1978-01-01

    Results of studies of the solvation shell structure of silver atoms in ice matrix at 4/sup 0/K by electron spin resonance (ESR) and electron spin echo spectrometry are reported. Drastic change in the hyperfine coupling constant of the silver atom was noted when the silver atom initially produced at 4/sup 0/K was warmed to 77/sup 0/K and reexamined by ESR at 4/sup 0/K. This suggested a very drastic rearrangement of the water molecules surrounding the silver atom. The geometric arrangement of water molecules around the silver atom produced at 4/sup 0/K was what would be expected for a solvated silver ion, indicating that no rearrangement had occurred after the silver atom formed. The addition of a little thermal excitation (heating to 77/sup 0/K) results in the geometry changes than can be explained by assuming either that a water molecule rotates around one of its OH bands or by the development of a hydrogen bond between the silver atom and one of the first solvation shell water molecules. Optical excitation in the absorption band of the silver atom in the ice matrix at 400nm resulted in desolvation of the silver ion or a reversion to the structure originally obtained by reaction of solver salts in ic matrix with radiation produced electrons. This was best explained by a charge transfer mechanism. (BLM)

  9. Recent results on solvation dynamics of electron and spur reactions of solvated electron in polar solvents studied by femtosecond laser spectroscopy and picosecond pulse radiolysis

    International Nuclear Information System (INIS)

    Mostafavi, M.

    2006-01-01

    Here, we report several studies done recently at ELYSE laboratory on the solvation dynamics of electron and on the kinetics of solvated electron in the spur reactions, performed by femtosecond laser spectroscopy and picosecond pulse radiolysis, respectively. Solvated electrons have been produced in polyol (1,2-Etanediol, 1,2-Propanediol and 1,3-Propanediol) by two-photon ionization of the solvent with 263 nm femtosecond laser pulses at room temperature. The two-photon absorption coefficient of these solvents at 263 nm has been determined. The dynamics of electron solvation in polyols has been studied by pump-probe transient absorption spectroscopy. So, time resolved absorption spectra ranging from 430 to 720 nm have been measured (Figure 1). A blue shift of the spectra is observed for the first tens of picoseconds. Using Bayesian data analysis method, the observed solvation dynamics are reconstructed with different models: stepwise mechanisms, continuous relaxation models or combinations of stepwise and continuous relaxation. That analysis clearly indicates that it is not obvious to select a unique model to describe the solvation dynamics of electron in diols. We showed that several models are able to reproduce correctly the data: a two-step model, a heterogeneous or bi-exponential continuous relaxation model and even a hybrid model with a stepwise transition and homogeneous continuous relaxation. Nevertheless, the best fits are given by the continuous spectral relaxation models. The fact that the time-evolution of the absorption spectrum of the solvated electron in diols can be accurately described by the temperature dependent absorption spectrum of the ground state solvated electron suggests that the spectral blue shift is mostly caused by the continuous relaxation of the electron trapped in a large distribution of solvent cages. Similar trends on electron solvation dynamics are observed in the cases of 1,2-ethanediol, 1,3-propanediol and 1,2 propanediol

  10. A solvated electron lithium electrode for secondary batteries

    Science.gov (United States)

    Sammells, A. F.; Semkow, K. W.

    1986-09-01

    Attention is given to a novel method for the achievement of high electro-chemical reversibility in Li-based nonaqueous cells, using a liquid negative electrode that consists of Li dissolved in liquid ammonia as a solvated electron Li electrode. The containment of this liquid negative active material from direct contact to a liquid nonaqueous electrolyte in the positive electrode compartment was realized through the use of a Li-intercalated, electronically conducting ceramic membrane.

  11. Comparison of solvation dynamics of electrons in four polyols

    Energy Technology Data Exchange (ETDEWEB)

    Lampre, I.; Pernot, P.; Bonin, J. [Laboratoire de Chimie Physique/ELYSE, Universite Paris-Sud 11, UMR 8000, Bat. 349, Orsay F-91405 (France); CNRS, Orsay F-91405 (France); Mostafavi, M. [Laboratoire de Chimie Physique/ELYSE, Universite Paris-Sud 11, UMR 8000, Bat. 349, Orsay F-91405 (France); CNRS, Orsay F-91405 (France)], E-mail: mehran.mostafavi@lcp.u-psud.fr

    2008-10-15

    Using pump-probe transient absorption spectroscopy, we studied the solvation dynamics of the electron in liquid polyalcohols: ethane-1,2-diol, propane-1,2-diol, propane-1,3-diol and propane-1,2,3-triol. Time-resolved absorption spectra ranging from 440 to 720 nm were measured. Our study shows that the excess electron in the diols presents an intense and wide absorption band in the visible and near-IR spectral domain at early time after two-photon ionization of the neat solvent. Then, for the first tens of picoseconds, the electron spectrum shifts toward the blue domain and its bandwidth decreases as the red part of the initial spectrum rapidly drops, while the blue part hardly evolves. In contrast, in the triol, the absorption spectrum of the electron is early situated in the visible range after the pump pulse and then solely evolves in the red part. The Bayesian data analysis of the observed picosecond solvation dynamics with different models is in favor of a heterogeneous continuous relaxation. That is corroborated by the analogy between the change in the absorption band with increasing time or decreasing temperature. That tends to indicate a similar organization disorder of the solvent. Moreover, the electron solvation dynamics is very fast in propane-1,2,3-triol despite its high viscosity and highlight the role of the OH-group in that process.

  12. Equilibrium and nonequilibrium solvation and solute electronic structure

    International Nuclear Information System (INIS)

    Kim, H.J.; Hynes, J.T.

    1990-01-01

    When a molecular solute is immersed in a polar and polarizable solvent, the electronic wave function of the solute system is altered compared to its vacuum value; the solute electronic structure is thus solvent-dependent. Further, the wave function will be altered depending upon whether the polarization of the solvent is or is not in equilibrium with the solute charge distribution. More precisely, while the solvent electronic polarization should be in equilibrium with the solute electronic wave function, the much more sluggish solvent orientational polarization need not be. We call this last situation non-equilibrium solvation. We outline a nonlinear Schroedinger equation approach to these issues

  13. Role of trapped and solvated electrons in Ps formation

    International Nuclear Information System (INIS)

    Stepanov, S.V.; Byakov, V.M.; Mikhin, K.V.; He, C.; Hirade, T.

    2005-01-01

    Role of trapped and solvated electrons in Ps formation is discussed. Combination of thermalized positron with such electrons is possible from the view point of the energy balance and may results in Ps formation. This process proceeds during all e = lifetime matter. Fitting of raw experimental e + -e - annihilation spectra has to be based on an adequate physical input, which often leads to necessity of nonexponential deconvolution of the spectra. We have interpreted the Ps formation data in polyethylene, ethylene-methylmethacrylate and polymethylmethacrylate in dark and in light vs. tome of the measurement and temperature. parameters characterized accumulation of trapped electrons and their recombination with counter ions and positrons are obtained. (author)

  14. Benzonitrile: Electron affinity, excited states, and anion solvation

    Science.gov (United States)

    Dixon, Andrew R.; Khuseynov, Dmitry; Sanov, Andrei

    2015-10-01

    We report a negative-ion photoelectron imaging study of benzonitrile and several of its hydrated, oxygenated, and homo-molecularly solvated cluster anions. The photodetachment from the unsolvated benzonitrile anion to the X ˜ 1 A 1 state of the neutral peaks at 58 ± 5 meV. This value is assigned as the vertical detachment energy (VDE) of the valence anion and the upper bound of adiabatic electron affinity (EA) of benzonitrile. The EA of the lowest excited electronic state of benzonitrile, a ˜ 3 A 1 , is determined as 3.41 ± 0.01 eV, corresponding to a 3.35 eV lower bound for the singlet-triplet splitting. The next excited state, the open-shell singlet A ˜ 1 A 1 , is found about an electron-volt above the triplet, with a VDE of 4.45 ± 0.01 eV. These results are in good agreement with ab initio calculations for neutral benzonitrile and its valence anion but do not preclude the existence of a dipole-bound state of similar energy and geometry. The step-wise and cumulative solvation energies of benzonitrile anions by several types of species were determined, including homo-molecular solvation by benzonitrile, hydration by 1-3 waters, oxygenation by 1-3 oxygen molecules, and mixed solvation by various combinations of O2, H2O, and benzonitrile. The plausible structures of the dimer anion of benzonitrile were examined using density functional theory and compared to the experimental observations. It is predicted that the dimer anion favors a stacked geometry capitalizing on the π-π interactions between the two partially charged benzonitrile moieties.

  15. Solvation of the electron in alcohols studied using the Argonne picosecond pulse radiolysis system

    International Nuclear Information System (INIS)

    Jonah, C.D.; Kenney-Wallace, G.A.

    1979-01-01

    With a stroboscopic pulse radiolysis system, it is possible to measure the reactions of solvated electrons and dry electrons and the solvation time of electrons in alcohols from 20 psec to 350 psec. The solvation in alcohol and alcohol-alkane solutions is a complex process which depends on the microscopic structure of the fluid, so that the studies of solvation in alcohols as a function of temperature or as a function of the concentration of the alcohols must take into account the structure of the fluid being studied. The relaxation processes may not be dominant at low temperature. However, in room temperature alcohols, pre-existing traps are the dominant means of electron trapping. The extrapolation to water may be reasonable since water and alcohols both give similar final species. To obtain such idea of the solvation process in alcohols, the change of the absorption of electrons at 500 nm was measured. At very low concentration of alcohols in alkanes, electrons form a complex with a cluster of alcohol molecules, and the most probable size of this cluster is two alcohols (C 4 , C 10 ). The species formed is not solvated electrons, since the characteristic spectrum of solvated electrons is absent, and the conductivity of the species is far above that of solvated electrons. (Yamashita, S.)

  16. Significance of solvated electrons (e(aq)-) as promoters of life on earth.

    Science.gov (United States)

    Getoff, Nikola

    2014-01-01

    Based on the present state of knowledge a new hypothesis concerning the origin of life on Earth is presented, and emphasizes the particular significance of solvated electrons (e(aq)(-)). Solvated electrons are produced in seawater, mainly by (40)K radiation and in atmospheric moisture by VUV light, electrical discharges and cosmic ray. Solvated electrons are involved in primary chemical processes and in biological processes. The conversion of aqueous CO2 and CO into simple organic substances, the generation of ammonia from N2 and water, the formation of amines, amino acids and simple proteins under the action of e(aq)(-) has been experimentally proven. Furthermore, it is supposed that the generation of the primitive cell and equilibria of primitive enzymes are also realized due to the strong reducing property of e(aq)(-). The presented hypothesis is mainly founded on recently obtained experimental results. The involvement of e(aq)(-) in such mechanisms, as well as their action as an initiator of life is also briefly discussed.

  17. Electron detachment energies in high-symmetry alkali halide solvated-electron anions

    Science.gov (United States)

    Anusiewicz, Iwona; Berdys, Joanna; Simons, Jack; Skurski, Piotr

    2003-07-01

    We decompose the vertical electron detachment energies (VDEs) in solvated-electron clusters of alkali halides in terms of (i) an electrostatic contribution that correlates with the dipole moment (μ) of the individual alkali halide molecule and (ii) a relaxation component that is related to the polarizability (α) of the alkali halide molecule. Detailed numerical ab initio results for twelve species (MX)n- (M=Li,Na; X=F,Cl,Br; n=2,3) are used to construct an interpolation model that relates the clusters' VDEs to their μ and α values as well as a cluster size parameter r that we show is closely related to the alkali cation's ionic radius. The interpolation formula is then tested by applying it to predict the VDEs of four systems [i.e., (KF)2-, (KF)3-, (KCl)2-, and (KCl)3-] that were not used in determining the parameters of the model. The average difference between the model's predicted VDEs and the ab initio calculated electron binding energies is less than 4% (for the twelve species studied). It is concluded that one can easily estimate the VDE of a given high-symmetry solvated electron system by employing the model put forth here if the α, μ and cation ionic radii are known. Alternatively, if VDEs are measured for an alkali halide cluster and the α and μ values are known, one can estimate the r parameter, which, in turn, determines the "size" of the cluster anion.

  18. 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

  19. Characterization of solvated electrons in hydrogen cyanide clusters: (HCN)n- (n=3, 4)

    Science.gov (United States)

    Wu, Di; Li, Ying; Li, Zhuo; Chen, Wei; Li, Zhi-Ru; Sun, Chia-Chung

    2006-02-01

    Theoretical studies of the solvated electrons (HCN)n- (n =3, 4) reveal a variety of electron trapping possibilities in the (HCN)n (n =3, 4) clusters. Two isomers for (HCN)3- and four isomers for (HCN)4- are obtained at the MP2/aug -cc-pVDZ+dBF (diffusive bond functions) level of theory. In view of vertical electron detachment energies (VDEs) at the CCSD(T) level, the excess electron always "prefers" locating in the center of the system, i.e., the isomer with higher coordination number shows larger VDE value. However, the most stable isomers of the solvated electron state (HCN)3- and (HCN)4- are found to be the linear C∞ν and D∞h structures, respectively, but not the fullyl symmetric structures which have the largest VDE values.

  20. Solvation of excess electrons trapped in charge pockets on molecular surfaces

    Science.gov (United States)

    Jalbout, Abraham F.

    This work considers the ability of hydrogen fluoride (HF) to solvate excess electrons located on cyclic hydrocarbon surfaces. The principle applied involves the formation of systems in which excess electrons can be stabilized not only on concentrated molecular surface charge pockets but also by HF. Recent studies have shown that OH groups can form stable hydrogen-bonded networks on one side of a hydrocarbon surface (i.e. cyclohexane sheets), at the same time, the hydrogen atoms on the opposite side of this surface form a pocket of positive charge can attract the excess electron. This density can be further stabilized by the addition of an HF molecule that can form an 'anion with an internally solvated electron' (AISE) state. These systems are shown to be stable with respect to vertical electron detachment (VDE).

  1. Photoinduced electron transfer and solvation in iodide-doped acetonitrile clusters.

    Science.gov (United States)

    Ehrler, Oli T; Griffin, Graham B; Young, Ryan M; Neumark, Daniel M

    2009-04-02

    We have used ultrafast time-resolved photoelectron imaging to measure charge transfer dynamics in iodide-doped acetonitrile clusters I(-)(CH(3)CN)(n) with n = 5-10. Strong modulations of vertical detachment energies were observed following charge transfer from the halide, allowing interpretation of the ongoing dynamics. We observe a sharp drop in the vertical detachment energy (VDE) within 300-400 fs, followed by a biexponential increase that is complete by approximately 10 ps. Comparison to theory suggests that the iodide is internally solvated and that photodetachment results in formation of a diffuse electron cloud in a confined cavity. We interpret the initial drop in VDE as a combination of expansion of the cavity and localization of the excess electron on one or two solvent molecules. The subsequent increase in VDE is attributed to a combination of the I atom leaving the cavity and rearrangement of the acetonitrile molecules to solvate the electron. The n = 5-8 clusters then show a drop in VDE of around 50 meV on a much longer time scale. The long-time VDEs are consistent with those of (CH(3)CN)(n)(-) clusters with internally solvated electrons. Although the excited-state created by the pump pulse decays by emission of a slow electron, no such decay is seen by 200 ps.

  2. Solvated electrons at elevated temperatures in different alcohols: Temperature and molecular structure effects

    Energy Technology Data Exchange (ETDEWEB)

    Yan, Yu [Department of Nuclear Engineering and Management, Graduate School of Engineering, University of Tokyo, 7-3-1 Hongo, Bunkyo, Tokyo 113-8656 (Japan); Lin, Mingzhang [Nuclear Science and Engineering Directorate, Japan Atomic Energy Agency, 2-4 Shirakata-Shirane, Tokai, Naka, Ibaraki 319-1195 (Japan); Katsumura, Yosuke, E-mail: katsu@n.t.u-tokyo.ac.j [Department of Nuclear Engineering and Management, Graduate School of Engineering, University of Tokyo, 7-3-1 Hongo, Bunkyo, Tokyo 113-8656 (Japan); Nuclear Professional School, Graduate School of Engineering, University of Tokyo, 2-22 Shirakata-Shirane, Tokai, Naka, Ibaraki 319-1188 (Japan); Fu, Haiying; Muroya, Yusa [Nuclear Professional School, Graduate School of Engineering, University of Tokyo, 2-22 Shirakata-Shirane, Tokai, Naka, Ibaraki 319-1188 (Japan)

    2010-12-15

    The absorption spectra of solvated electrons in pentanol, hexanol and octanol are measured from 22 to 200, 22 to 175 and 50 to150 {sup o}C, respectively, at a fixed pressure of 15 MPa, using nanosecond pulse radiolysis technique. The results show that the peak positions of the absorption spectra have a red-shift (shift to longer wavelengths) as temperature increases, similar to water and other alcohols. Including the above mentioned data, a compilation of currently available experimental data on the energy of absorption maximum (E{sub max}) of solvated electrons changed with temperature in monohydric alcohols, diols and triol is presented. E{sub max} of solvated electron is larger in those alcohols that have more OH groups at all the temperatures. The molecular structure effect, including OH numbers, OH position and carbon chain length, is investigated. For the primary alcohols with same OH group number and position, the temperature coefficient increases with increase in chain length. For the alcohols with same chain length and OH numbers, temperature coefficient is larger for the symmetric alcohols than the asymmetric ones.

  3. Pulse radiolysis study in ethanol and N-propanol of the solvated electron formation and reactivity at low temperatures

    International Nuclear Information System (INIS)

    Bono Merino, M.R.

    1978-01-01

    The electron solvation process in polar media has been studied in liquid ethanol and n-propanol at temperatures near their melting points. The results show that using the change of absorption at a given wavelength to determine the solvation time leads to a value which varies with the wavelength considered. Furthermore, for n-propanol it appears that the process occurs without a definite order. Studies of the spectral shifts show that the passage from the initial to the final spectrum (solvated electron spectrum) involves intermediate transient spectra which probably correspond to partly solvated states of the electron. The interpretation of these various results points out the ambiguity of the kinetic measurements: the simultaneous existence of several partly solvated states of the electron is not consistent with the hypothesis previously admitted that the molar extinction coefficient at a given wavelength is unique and does not vary with time. The reaction of the solvated electron with acetone has been studied in ethanol in the temperature range from +25 to -105 0 C: this reaction is diffusion controlled [fr

  4. Pulse radiolysis study on solvated electrons in ionic liquid with controlling water content

    International Nuclear Information System (INIS)

    Yang Jinfeng; Kondoh, T.; Yoshida, Y.; Nagaishi, R.

    2006-01-01

    Room-temperature ionic liquids, which are nonvolatile and nonflammable, have been proposed as 'green solvents' for new applications in chemical synthesis, separation chemistry, electrochemistry and other areas. In the separation chemistry, the hydrophobic ionic liquids have been practically expected to be alternative to traditional organic solvents for solvent extraction of 4f and 5f elements from the viewpoints of the immiscibility in water, especially in the spent nuclear fuel reprocessing. However, the chemical reaction or kinetics studies are important to apply the ionic liquids for various processes. To understand the effects of ionic liquids on chemical reactions, pulse radiolysis studies of ionic liquid have been carried out on nanosecond scale by using a 27 MeV electron beam and an analyzing light source of xenon lamp. In the experiment, a hydrophobic ionic liquid of diethylmethyl(2-methoxy)ammonium-bis(trifluoromethanesulfonyl)imide (DEMMA-TFSI) salt was used. The ionic liquid of DEMMA-TFSI was prepared by reacting equimolar amounts of diethylmethyl(2-methoxy)ammonium chloride (C 10 H 20 F 6 N 2 O 5 S 2 Cl, >98%, Nisshinbo) with lithium bis(trifluoromethanesulfonyl)imide (LiN(SO 2 CF 3 ) 2 , SynQuest Labs., Inc.) in aqueous solutions at room temperature. The ionic liquid was separated from the aqueous phase, purified by repeated extractions with water to LiCl and excess reagent, and finally dried at 110 degree C under vacuum. The transient absorptions of the ionic liquid were measured at wavelengths from 350 to 1400 nm, in which two photodiodes of silicon ( 1000 nm) were used. The spectrum of solvated electrons in the ionic liquid of DEMMA-TFSI was obtained with an absorption peak of 1060 nm and a wide bandwidth of about 600 nm (FWHM). The decay constant of the solvated electrons in the ionic liquid was 1.54 x 10 7 s -1 , which is independent on the wavelength. The absorption peak of the spectrum was blue-shifted from 1060 to 780 nm with increasing water

  5. Photo-illuminated diamond as a solid-state source of solvated electrons in water for nitrogen reduction.

    Science.gov (United States)

    Zhu, Di; Zhang, Linghong; Ruther, Rose E; Hamers, Robert J

    2013-09-01

    The photocatalytic reduction of N₂ to NH₃ is typically hampered by poor binding of N₂ to catalytic materials and by the very high energy of the intermediates involved in this reaction. Solvated electrons directly introduced into the reactant solution can provide an alternative pathway to overcome such limitations. Here we demonstrate that illuminated hydrogen-terminated diamond yields facile electron emission into water, thus inducing reduction of N₂ to NH₃ at ambient temperature and pressure. Transient absorption measurements at 632 nm reveal the presence of solvated electrons adjacent to the diamond after photoexcitation. Experiments using inexpensive synthetic diamond samples and diamond powder show that photocatalytic activity is strongly dependent on the surface termination and correlates with the production of solvated electrons. The use of diamond to eject electrons into a reactant liquid represents a new paradigm for photocatalytic reduction, bringing electrons directly to reactants without requiring molecular adsorption to the surface.

  6. Negative ion photoelectron spectroscopy of solvated electron cluster anions, (H2O)n- and (NH3)n-

    International Nuclear Information System (INIS)

    Lee, G.H.; Arnold, S.T.; Eaton, J.G; Sarkas, H.W.; Bowen, K.H.; Ludewigt, C.; Haberland, H.

    1991-01-01

    The photodetachment spectra of (H 2 O) - n=2-69 and (NH 3 ) - n=41-1100 have been recorded, and vertical detachment energies (VDEs) were obtained from the spectra. For both systems, the cluster anion VDEs increase smoothly with increasing sizes and most species plot linearly with n -1/3 , extrapolating to a VDE (n = ∞) value which is very close to the photoelectric threshold energy for the corresponding condensed phase solvated electron system. The linear extrapolation of this data to the analogous condensed phase property suggests that these cluster anions are gas phase counterparts to solvated electrons, i.e. they are embryonic forms of hydrated and ammoniated electrons which mature with increasing cluster size toward condensed phase solvated electrons. (orig.)

  7. Negative ion photoelectron spectroscopy of solvated electron cluster anions, (H2O){/n -} and (NH3){/n -}

    Science.gov (United States)

    Lee, G. H.; Arnold, S. T.; Eaton, J. G.; Sarkas, H. W.; Bowen, K. H.; Ludewigt, C.; Haberland, H.

    1991-03-01

    The photodetachment spectra of (H2O){/n =2-69/-} and (NH3){/n =41-1100/-} have been recorded, and vertical detachment energies (VDEs) were obtained from the spectra. For both systems, the cluster anion VDEs increase smoothly with increasing sizes and most species plot linearly with n -1/3, extrapolating to a VDE ( n=∞) value which is very close to the photoelectric threshold energy for the corresponding condensed phase solvated electron system. The linear extrapolation of this data to the analogous condensed phase property suggests that these cluster anions are gas phase counterparts to solvated electrons, i.e. they are embryonic forms of hydrated and ammoniated electrons which mature with increasing cluster size toward condensed phase solvated electrons.

  8. Network topology for the formation of solvated electrons in binary CaO–Al2O3 composition glasses

    Science.gov (United States)

    Akola, Jaakko; Kohara, Shinji; Ohara, Koji; Fujiwara, Akihiko; Watanabe, Yasuhiro; Masuno, Atsunobu; Usuki, Takeshi; Kubo, Takashi; Nakahira, Atsushi; Nitta, Kiyofumi; Uruga, Tomoya; Weber, J. K. Richard; Benmore, Chris J.

    2013-01-01

    Glass formation in the CaO–Al2O3 system represents an important phenomenon because it does not contain typical network-forming cations. We have produced structural models of CaO–Al2O3 glasses using combined density functional theory–reverse Monte Carlo simulations and obtained structures that reproduce experiments (X-ray and neutron diffraction, extended X-ray absorption fine structure) and result in cohesive energies close to the crystalline ground states. The O–Ca and O–Al coordination numbers are similar in the eutectic 64 mol % CaO (64CaO) glass [comparable to 12CaO·7Al2O3 (C12A7)], and the glass structure comprises a topologically disordered cage network with large-sized rings. This topologically disordered network is the signature of the high glass-forming ability of 64CaO glass and high viscosity in the melt. Analysis of the electronic structure reveals that the atomic charges for Al are comparable to those for Ca, and the bond strength of Al–O is stronger than that of Ca–O, indicating that oxygen is more weakly bound by cations in CaO-rich glass. The analysis shows that the lowest unoccupied molecular orbitals occurs in cavity sites, suggesting that the C12A7 electride glass [Kim SW, Shimoyama T, Hosono H (2011) Science 333(6038):71–74] synthesized from a strongly reduced high-temperature melt can host solvated electrons and bipolarons. Calculations of 64CaO glass structures with few subtracted oxygen atoms (additional electrons) confirm this observation. The comparable atomic charges and coordination of the cations promote more efficient elemental mixing, and this is the origin of the extended cage structure and hosted solvated (trapped) electrons in the C12A7 glass. PMID:23723350

  9. Estimate of electrostatic solvation free energy of electron in various polar solvents by using modified born equation

    International Nuclear Information System (INIS)

    Yamashita, Kazuo; Kitamura, Mitsutaka; Imai, Hideo

    1976-01-01

    The modified Born equation was tentatively applied to estimate the electrostatic free energies of solvation of the electron in various polar solvents. The related data of halide ions and a datum of the hydration free energy of the electron obtained by radiation chemical studies were used for the numerical calculations. (auth.)

  10. Structural and dynamical properties of solvated electrons; a study of kinetic spectroscopy using pulse radiolysis

    International Nuclear Information System (INIS)

    Huis, C. van

    1977-01-01

    In this thesis the pulse radiolysis experiments of hexamethyl-phosphortriamide (HMPA), propanol-1, 3-methylpentane and mixtures of propanol-1 and 3-methylpentane are reported. In the pulse radiolysis of HMPA, carried out at room temperature, the high yield of esub(s) - (G=2) and the very high wavelength of the maximum absorption (max= 2200 nm) in the esub(s) - absorption spectrum are explained by considering the aprotic nature and the molecular structure of this compound. In the experiment with propanol-1 (temperature range 93deg-123degK) a temporal shift to lower wavelengths in the time range of 10 s-10 ms is observed. In further experiments biphenyl was used as electron scavenger. It was concluded that after the electron pulse the following sequence of events takes place: 1) electron redistribution in times shorter than 1 s; 2) dipole reorientation during 10 s-10 ms; 3) recombination of a part of the solvated electrons; 4) a reaction of the solvated electrons with the neighbouring propanol-1 molecules. In the experiments with 3-methylpentane at 103deg-113degK an esub(s) - absorption band with third order decay kinetics was observed. This is attributed to geminate recombination. The activation energy of the recombination process was 0.4 eV. The experiments with mixtures of propanol-1 and 3-methylpentane were carried out at 103degK. At low propanol-1 concentrations the build-up at 500 nm obeys first order kinetics, whereas at high concentrations this build-up can be split up into three first order components, as was measured in pure propanol-1. The half-lives of the three components were in the ratio of 1:10:100. In the last chapter theoretical models for the electron redistribution and the matric relaxation are discussed and compared with the experiments

  11. The reactivity of allyl and propargyl alcohols with solvated electrons: temperature and solvent effects

    International Nuclear Information System (INIS)

    Afanassiev, A.M.; Okazaki, K.; Freeman, G.R.

    1979-01-01

    The rate constants K 1 for the reaction of solvated electrons with allyl alcohol in a number of hydroxylic solvents differ by up to two orders of magnitude and decrease in the order tert-butyl alcohol > 2-propanol > l-propanol approximately ethanol > methanol approximately ethylene glycol > water. In methanol and ethylene glycol the rate constants (7 x 10 7 M -1 s -1 at 298 K) and activation energies (16 kJ/mol) are equal, in spite of a 32-fold difference in solvent viscosity (0.54 and 17.3 cP, respectively) and 3-fold difference in its activation energy (11 and 32 kJ/mol, respectively). The reaction in tert-butyl alcohol is nearly diffusion controlled and has a high activation energy that is characteristic of transport in that liquid (E 1 = 31 kJ/mol, E sub(eta) = 39 kJ/mol). The activation energies in the other alcohols are all 16 kJ/mol, and it is 14 kJ/mol in water. They do not correlate with transport properties. The solvent effect is connected primarily with the entropy of activation. The rate constants correlate with the solvated electron trap depth. When the electron affinity of the scavenger is small, a favorable configuration of solvent molecules about the electron/scavenger encounter pair is required for the electron jump to take place. The behavior of the rate parameters for propargyl alcohol is similar to that for allyl alcohol, but k 1 , A 1 , and E 1 are larger for the former. The ratio k(propargyl)/k(allyl) at 298 K equals 10.5 in water and decreases through the series, reaching 1.3 in tert-butyl alcohol. Rate parameters for several other scavengers are also reported. (author)

  12. Band resolution of optical spectra of solvated electrons in water, alcohols, and tetrahydrofuran

    International Nuclear Information System (INIS)

    Jou, F.-Y.; Freeman, G.R.

    1979-01-01

    The optical absorption spectra of solvated electrons in water, alcohols, and tetrahydrofuran are empirically resolved into two Gaussian bands and a continuum tail. The first Gaussian band covers most of the low energy side of the spectrum. The second Gaussian band lies at an energy slightly above that of the absorption maximum of the total spectrum. With the exception of tert-butyl alcohol, in water and alcohols the following were observed: (a) the first Gaussian bands have the same half-width, but the oscillator strength in water is about double that in an alcohol; (b) the second Gaussian bands have similar half-widths and oscillator strengths; (c) the continuum tails have similar half-widths, yet that in water possesses only about one third as much oscillator strength as the one in alcohol. In tert-butyl alcohol and tetrahydrofuran the first Gaussian band and the continuum tail each carry nearly half of the total oscillator strength. (author)

  13. Solvated electron: criticism of a suggested correlation of chemical potential with optical absorption energy

    International Nuclear Information System (INIS)

    Farhataziz, M.

    1984-01-01

    A recent theoretical treatment of the absorption spectrum of the solvated electron, e - sub(s), maintains that rigorously μ 0 >= -0.75 Esub(av), which gives empirical relationship, μ 0 >= -(0.93 +- 0.02)Esub(max). For e - sub(s) in a particular solvent at a temperature and pressure, μ 0 , Esub(av) and Esub(max) are standard chemical potential, average energy of the absorption spectrum and the energy at the absorption maximum respectively. The temperature and pressure effects on the absorption spectrum of e - sub(s) in water and liquid ammonia do not support the equality sign in the above cited relationships. The implications of inequality expressed above are discussed for e - sub(s) in water and liquid ammonia. (author)

  14. Dynamics of electron solvation in methanol: Excited state relaxation and generation by charge-transfer-to-solvent

    International Nuclear Information System (INIS)

    Elkins, Madeline H.; Williams, Holly L.; Neumark, Daniel M.

    2015-01-01

    The charge-transfer-to-solvent dynamics (CTTS) and excited state relaxation mechanism of the solvated electron in methanol are studied by time-resolved photoelectron spectroscopy on a liquid methanol microjet by means of two-pulse and three-pulse experiments. In the two-pulse experiment, CTTS excitation is followed by a probe photoejection pulse. The resulting time-evolving photoelectron spectrum reveals multiple time scales characteristic of relaxation and geminate recombination of the initially generated electron which are consistent with prior results from transient absorption. In the three-pulse experiment, the relaxation dynamics of the solvated electron following electronic excitation are measured. The internal conversion lifetime of the excited electron is found to be 130 ± 40 fs, in agreement with extrapolated results from clusters and the non-adiabatic relaxation mechanism

  15. Dynamics of electron solvation in methanol: Excited state relaxation and generation by charge-transfer-to-solvent

    Science.gov (United States)

    Elkins, Madeline H.; Williams, Holly L.; Neumark, Daniel M.

    2015-06-01

    The charge-transfer-to-solvent dynamics (CTTS) and excited state relaxation mechanism of the solvated electron in methanol are studied by time-resolved photoelectron spectroscopy on a liquid methanol microjet by means of two-pulse and three-pulse experiments. In the two-pulse experiment, CTTS excitation is followed by a probe photoejection pulse. The resulting time-evolving photoelectron spectrum reveals multiple time scales characteristic of relaxation and geminate recombination of the initially generated electron which are consistent with prior results from transient absorption. In the three-pulse experiment, the relaxation dynamics of the solvated electron following electronic excitation are measured. The internal conversion lifetime of the excited electron is found to be 130 ± 40 fs, in agreement with extrapolated results from clusters and the non-adiabatic relaxation mechanism.

  16. Dynamics of electron solvation in methanol: Excited state relaxation and generation by charge-transfer-to-solvent

    Energy Technology Data Exchange (ETDEWEB)

    Elkins, Madeline H.; Williams, Holly L. [Department of Chemistry, University of California, Berkeley, California 94720 (United States); Neumark, Daniel M. [Department of Chemistry, University of California, Berkeley, California 94720 (United States); Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720 (United States)

    2015-06-21

    The charge-transfer-to-solvent dynamics (CTTS) and excited state relaxation mechanism of the solvated electron in methanol are studied by time-resolved photoelectron spectroscopy on a liquid methanol microjet by means of two-pulse and three-pulse experiments. In the two-pulse experiment, CTTS excitation is followed by a probe photoejection pulse. The resulting time-evolving photoelectron spectrum reveals multiple time scales characteristic of relaxation and geminate recombination of the initially generated electron which are consistent with prior results from transient absorption. In the three-pulse experiment, the relaxation dynamics of the solvated electron following electronic excitation are measured. The internal conversion lifetime of the excited electron is found to be 130 ± 40 fs, in agreement with extrapolated results from clusters and the non-adiabatic relaxation mechanism.

  17. Dynamics of electron solvation in I-(CH3OH)n clusters (4 ≤n≤ 11)

    International Nuclear Information System (INIS)

    Young, Ryan M.; Yandell, Margaret A.; Neumark, Daniel M.

    2011-01-01

    The dynamics of electron solvation following excitation of the charge-transfer-to-solvent precursor state in iodide-doped methanol clusters, I - (CH 3 OH) n=4-11 , are studied with time-resolved photoelectron imaging. This excitation produces a I ... (CH 3 OH) n - cluster that is unstable with respect to electron autodetachment and whose autodetachment lifetime increases monotonically from ∼800 fs to 85 ps as n increases from 4 to 11. The vertical detachment energy (VDE) and width of the excited state feature in the photoelectron spectrum show complex time dependence during the lifetime of this state. The VDE decreases over the first 100-400 fs, then rises exponentially to a maximum with a ∼1 ps time constant, and finally decreases by as much as 180 meV with timescales of 3-20 ps. The early dynamics are associated with electron transfer from the iodide to the methanol cluster, while the longer-time changes in VDE are attributed to solvent reordering, possibly in conjunction with ejection of neutral iodine from the cluster. Changes in the observed width of the spectrum largely follow those of the VDEs; the dynamics of both are attributed to the major rearrangement of the solvent cluster during relaxation. The relaxation dynamics are interpreted as a reorientation of at least one methanol molecule and the disruption and formation of the solvent network in order to accommodate the excess charge.

  18. Dynamics of electron solvation in I(-)(CH3OH)n clusters (4 ≤ n ≤ 11).

    Science.gov (United States)

    Young, Ryan M; Yandell, Margaret A; Neumark, Daniel M

    2011-03-28

    The dynamics of electron solvation following excitation of the charge-transfer-to-solvent precursor state in iodide-doped methanol clusters, I(-)(CH(3)OH)(n = 4-11), are studied with time-resolved photoelectron imaging. This excitation produces a I···(CH(3)OH)(n)(-) cluster that is unstable with respect to electron autodetachment and whose autodetachment lifetime increases monotonically from ~800 fs to 85 ps as n increases from 4 to 11. The vertical detachment energy (VDE) and width of the excited state feature in the photoelectron spectrum show complex time dependence during the lifetime of this state. The VDE decreases over the first 100-400 fs, then rises exponentially to a maximum with a ~1 ps time constant, and finally decreases by as much as 180 meV with timescales of 3-20 ps. The early dynamics are associated with electron transfer from the iodide to the methanol cluster, while the longer-time changes in VDE are attributed to solvent reordering, possibly in conjunction with ejection of neutral iodine from the cluster. Changes in the observed width of the spectrum largely follow those of the VDEs; the dynamics of both are attributed to the major rearrangement of the solvent cluster during relaxation. The relaxation dynamics are interpreted as a reorientation of at least one methanol molecule and the disruption and formation of the solvent network in order to accommodate the excess charge.

  19. Irreversible electron attachment--a key to DNA damage by solvated electrons in aqueous solution.

    Science.gov (United States)

    Westphal, K; Wiczk, J; Miloch, J; Kciuk, G; Bobrowski, K; Rak, J

    2015-11-07

    The TYT and TXT trimeric oligonucleotides, where X stands for a native nucleobase, T (thymine), C (cytosine), A (adenine), or G (guanine), and Y indicates a brominated analogue of the former, were irradiated with ionizing radiation generated by a (60)Co source in aqueous solutions containing Tris as a hydroxyl radical scavenger. In the past, these oligomers were bombarded with low energy electrons under an ultra-high vacuum and significant damage to TXT trimers was observed. However, in aqueous solution, hydrated electrons do not produce serious damage to TXT trimers although the employed radiation dose exceeded many times the doses used in radiotherapy. Thus, our studies demonstrate unequivocally that hydrated electrons, which are the major form of electrons generated during radiotherapy, are a negligible factor in damage to native DNA. It was also demonstrated that all the studied brominated nucleobases have a potential to sensitize DNA under hypoxic conditions. Strand breaks, abasic sites and the products of hydroxyl radical attachment to nucleobases have been identified by HPLC and LC-MS methods. Although all the bromonucleobases lead to DNA damage under the experimental conditions of the present work, bromopyrimidines seem to be the radiosensitizers of choice since they lead to more strand breaks than bromopurines.

  20. Freezing hot electrons. Electron transfer and solvation dynamics at D{sub 2}O and NH{sub 3}-metal interfaces

    Energy Technology Data Exchange (ETDEWEB)

    Staehler, A.J.

    2007-05-15

    The present work investigates the electron transfer and solvation dynamics at the D{sub 2}O/Cu(111), D{sub 2}O/Ru(001), and NH{sub 3}/Cu(111) interfaces using femtosecond time-resolved two-photon photoelectron spectroscopy. Within this framework, the influence of the substrate, adsorbate structure and morphology, solvation site, coverage, temperature, and solvent on the electron dynamics are studied, yielding microscopic insight into the underlying fundamental processes. Transitions between different regimes of ET, substrate-dominated, barrier-determined, strong, and weak coupling are observed by systematic variation of the interfacial properties and development of empirical model descriptions. It is shown that the fundamental steps of the interfacial electron dynamics are similar for all investigated systems: Metal electrons are photoexcited to unoccupied metal states and transferred into the adlayer via the adsorbate's conduction band. The electrons localize at favorable sites and are stabilized by reorientations of the surrounding polar solvent molecules. Concurrently, they decay back two the metal substrate, as it offers a continuum of unoccupied states. However, the detailed characteristics vary for the different investigated interfaces: For amorphous ice-metal interfaces, the electron transfer is initially, right after photoinjection, dominated by the substrate's electronic surface band structure. With increasing solvation, a transient barrier evolves at the interface that increasingly screens the electrons from the substrate. Tunneling through this barrier becomes the rate-limiting step for ET. The competition of electron decay and solvation leads to lifetimes of the solvated electrons in the order of 100 fs. Furthermore, it is shown that the electrons bind in the bulk of the ice layers, but on the edges of adsorbed D{sub 2}O clusters and that the ice morphology strongly influences the electron dynamics. For the amorphous NH{sub 3}/Cu(111

  1. Time-dependent radiolytic yields at room temperature and temperature-dependent absorption spectra of the solvated electrons in polyols

    International Nuclear Information System (INIS)

    Lin Mingzhang; Mostafavi, M.; Lampre, I.; Muroya, Y.; Katsumura, Y.

    2007-01-01

    The molar extinction coefficients at the absorption maximum of the solvated electron spectrum have been evaluated to be 900, 970, and 1000 mol -1 ·m 2 for 1,2-ethanediol (12ED), 1,2-propanediol (12PD), and 1,3-propanediol (13PD), respectively. These values are two-third or three-fourth of the value usually reported in the published report. Picosecond pulse radiolysis studies have aided in depicting the radiolytic yield of the solvated electron in these solvents as a function of time from picosecond to microsecond. The radiolytic yield in these viscous solvents is found to be strongly different from that of the water solution. The temperature dependent absorption spectra of the solvated electron in 12ED, 12PD, and 13PD have been also investigated. In all the three solvents, the optical spectra shift to the red with increasing temperature. While the shape of the spectra does not change in 13PD, a widening on the blue side of the absorption band is observed in 12ED and 12PD at elevated temperatures. (authors)

  2. Effects of functional group substitution on electron spectra and solvation dynamics in a family of ionic liquids

    International Nuclear Information System (INIS)

    Wishart, James F.; Lall-Ramnarine, Sharon I.; Raju, Ravinder; Scumpia, Alexander; Bellevue, Sherly; Ragbir, Revans; Engel, Robert

    2005-01-01

    Ionic liquids containing ether-, alcohol- and alkyl-functionalized quaternary ammonium dications were studied by pulse radiolysis. Spectra on nanosecond timescales revealed that solvation of the excess electron is particularly slow in the case of the alcohol-derivatized ionic liquids. The blue shift of the electron spectrum to the customary 650 nm peak takes 25-40 ns at 21 deg. C. Comparison with the relaxation dynamics observed in viscous 1,2,6-trihydroxyhexane reveals the hindering effect of the ionic liquid lattice on hydroxypropyl side chain reorientation

  3. Contribution to the study of solvated electrons in water and alcohols and of radiolytic processes in organic carbonates by picosecond pulse radiolysis

    International Nuclear Information System (INIS)

    Torche, Faycal

    2012-01-01

    This work is part of the study area of the interaction of radiation with polar liquids. Using the picosecond electron accelerator ELYSE, studies were conducted using the techniques of pulse radiolysis combined with absorption spectrophotometry Time-resolved in the field of a picosecond. This work is divided into two separate chapters. The first study addresses the temporal variation of the radiolytic yield of solvated electron in water and simple alcohols. Due to original detection system mounted on the accelerator ELYSE, composed of a flash lamp specifically designed for the detection and a streak-camera used for the first time in absorption spectroscopy, it was possible to record the time-dependent radiolytic yields of the solvated electron from ten picoseconds to a few hundred nanoseconds. The scavenging of the electron solvated by methyl viologen, was utilized to reevaluate the molar extinction coefficient of the absorption spectrum of solvated electron in water and ethanol from isobestic points which corresponds to the intersection of the absorption spectra of solvated electron which disappears and methyl viologen which is formed during the reaction. The second chapter is devoted to the study of liquid organic carbonates such as dimethyl carbonate (DMC), diethyl carbonate (DEC) and propylene carbonate (PC). This family of carbonate which compose the electrolytes lithium batteries, has never been investigated by pulse radiolysis. The studies were focused on the PC in the light of these physicochemical characteristics, including its very high dielectric constant and its strong dipole moment of 4.9 D. The first results were obtained on aqueous solutions containing propylene carbonate to observe the reactions of reduction and oxidation of PC by radiolytic species of water (solvated electron and OH radicals). Then, after the identification (spectral and kinetic) of the species formed by interaction with the OH radical as the PC* radical resulting from the

  4. Effect of Solvation on Electron Detachment and Excitation Energies of a Green Fluorescent Protein Chromophore Variant.

    Science.gov (United States)

    Bose, Samik; Chakrabarty, Suman; Ghosh, Debashree

    2016-05-19

    Hybrid quantum mechanics/molecular mechanics (QM/MM) is applied to the fluorinated green fluorescent protein (GFP) chromophore (DFHBDI) in its deprotonated form to understand the solvatochromic shifts in its vertical detachment energy (VDE) and vertical excitation energy (VEE). This variant of the GFP chromophore becomes fluorescent in an RNA environment and has a wide range of applications in biomedical and biochemical fields. From microsolvation studies, we benchmark (with respect to full QM) the accuracy of our QM/MM calculations with effective fragment potential (EFP) as the MM method of choice. We show that while the solvatochromic shift in the VEE is minimal (0.1 eV blue shift) and its polarization component is only 0.03 eV, the effect of the solvent on the VDE is quite large (3.85 eV). We also show by accurate calculations on the solvatochromic shift of the VDE that polarization accounts for ∼0.23 eV and therefore cannot be neglected. The effect of the counterions on the VDE of the deprotonated chromophore in solvation is studied in detail, and a charge-smearing scheme is suggested for charged chromophores.

  5. Solvation thermodynamics

    CERN Document Server

    Ben-Naim, Arieh

    1987-01-01

    This book deals with a subject that has been studied since the beginning of physical chemistry. Despite the thousands of articles and scores of books devoted to solvation thermodynamics, I feel that some fundamen­ tal and well-established concepts underlying the traditional approach to this subject are not satisfactory and need revision. The main reason for this need is that solvation thermodynamics has traditionally been treated in the context of classical (macroscopic) ther­ modynamics alone. However, solvation is inherently a molecular pro­ cess, dependent upon local rather than macroscopic properties of the system. Therefore, the starting point should be based on statistical mechanical methods. For many years it has been believed that certain thermodynamic quantities, such as the standard free energy (or enthalpy or entropy) of solution, may be used as measures of the corresponding functions of solvation of a given solute in a given solvent. I first challenged this notion in a paper published in 1978 b...

  6. Detection of Intramolecular Charge Transfer and Dynamic Solvation in Eosin B by Femtosecond Two-Dimensional Electronic Spectroscopy

    Science.gov (United States)

    Ghosh, Soumen; Roscioli, Jerome D.; Beck, Warren F.

    2014-06-01

    We have employed 2D electronic photon echo spectroscopy to study intramolecular charge-transfer dynamics in eosin B. After preparation of the first excited singlet state (S_1) with 40-fs excitation pulses at 520 nm, the nitro group (--NO_2) in eosin B undergoes excited state torsional motion towards a twisted intramolecular charge transfer (TICT) state. As the viscosity of the surrounding solvent increases, the charge-transfer rate decreases because the twisting of the --NO_2 group is hindered. These conclusions are supported by the time evolution of the 2D spectrum, which provides a direct measure of the the ground-to-excited-state energy gap time-correlation function, M(t). In comparison to the inertial and diffusive solvation time scales exhibited by eosin Y, which lacks the nitro group, the M(t) function for eosin B exhibits under the same conditions an additional component on the 150-fs timescale that arises from quenching of the S_1 state by crossing to the TICT state. These results indicate that 2D electronic spectroscopy can be used as a sensitive probe of the rate of charge transfer in a molecular system and of the coupling to the motions of the surrounding solvent. (Supported by grant DE-SC0010847 from the Department of Energy, Office of Basic Energy Sciences, Photosynthetic Systems program.)

  7. Reduction of uranium(IV) and its mixtures with an olefin or an alkyne in tetrahydrofuran solutions by solvated electrons

    International Nuclear Information System (INIS)

    Koulkes-Pujo, A.M.; Le Marechal, J.F.; Le Motais, B.; Folcher, G.

    1985-01-01

    The reduction of UCl 4 and its mixtures with different olefins (stilbene, St, diphenylethylene, DPE, acenaphtylene, Ac or with diphenylacetylene (DPA) was studied by pulse radiolysis of tetrahydrofuran (THF) solutions. U(III) was formed by U(IV) reaction either with the solvated electrons created by THF radiolysis or with the transitory anions St - and DPA - . In the latter case, the reaction proceeds via a first step leading to [St-U(IV)] - or [DPA-U(IV)] - . In the case of DPE - the first species, [DPE-U(IV)] - , does not lead to U(III) but is destroyed by THF(H) + giving DPE(H). and U(IV). Ac - does not react with U(IV). A mechanistic scheme of this electron attachment is discussed as well as its implication in catalytic hydrogenation of olefins in LiAlH 4 -UCl 4 solutions. It is concluded that the catalytic effect observed is rather the result of a hydride transfer from a uranium transient compound to the alkenes. 22 references, 8 figures, 1 table

  8. Solvation effect on isomer stability and electronic structures of protonated serotonin

    Science.gov (United States)

    Omidyan, Reza; Amanollahi, Zohreh; Azimi, Gholamhassan

    2017-07-01

    Microsolvation effect on geometry and transition energies of protonated serotonin has been investigated by MP2 and CC2 quantum chemical methods. Also, conductor-like screening model, implemented recently in the MP2 and ADC(2) methods, was examined to address the bulk water environment's effect on the isomer stability and electronic transition energies of protonated serotonin. It has been predicted that the dipole moment of gas phase isomers plays the main role on the isomer stabilization in water solution and electronic transition shifts. Also, both red- and blue-shift effects have been predicted to take place on electronic transition energies, upon hydration.

  9. Radiation produced by electrons incident on molecules

    International Nuclear Information System (INIS)

    Moehlman, G.R.

    1977-01-01

    The work described in this thesis deals with light intensity measurements of emission spectra (1850-9000 A) produced by a continuous or pulsed beam of monoenergetic electrons (0 - 2000 eV) incident on a variety of molecular gases like H 2 , D 2 , H 2 O, HCl, NH 3 and several hydrocarbons. The emission spectra are dominated by fluorescence from excited fragments produced via dissociative excitation, besides fluorescence from excited parent molecules themselves. The experimental results thus obtained are expressed in terms of emission cross sections and lifetimes

  10. Imaging of block copolymer vesicles in solvated state by wet scanning transmission electron microscopy

    Czech Academy of Sciences Publication Activity Database

    Šlouf, Miroslav; Lapčíková, Monika; Štěpánek, M.

    2011-01-01

    Roč. 47, č. 6 (2011), s. 1273-1278 ISSN 0014-3057 R&D Projects: GA ČR GAP208/10/0353; GA AV ČR KAN200520704; GA AV ČR IAA400500703 Institutional research plan: CEZ:AV0Z40500505 Keywords : environmental scanning electron microscopy * self-assembly * amphiphilic block copolymers Subject RIV: CD - Macromolecular Chemistry Impact factor: 2.739, year: 2011

  11. Temperature and isotope effects on the shape of the optical absorption spectrum of solvated electrons in water

    International Nuclear Information System (INIS)

    Jou, F.Y.; Freeman, G.R.

    1979-01-01

    The optical absorption spectra of solvated electrons in H 2 O and D 2 O have been measured at 274, 298, 340, and 380 K. All the spectra were fitted very well with the Gaussian and Lorentzian shape functions at the low- and high-energy sides of the absorption maximum, respectively, excluding the high-energy tail. The spectrum does not shift uniformly with temperature. The temperature coefficient of absorption decreases rapidly with increasing energy on the low-energy side of the absorption maximum, while it changes only slightly on the high-energy side. When the temperature increases the Lorentzian width remains constant, the Gaussian width varies proportionally to T/sup 1/2/, and the spectrum becomes more symmetrical. On going from H 2 O to D 2 O we found that the spectrum at a given A/A/sub max/ shows a shift of +0.05 eV in the low-energy wing. The shift decreases with increasing energy, reaching 0.03 eV at the absorption maximum. On the high-energy side of the band the shift becomes negative at hν > 2.2 eV. The shift on the low-energy side seems to be related to the difference of the zero-point energies of the inter- and intramolecular vibrations. The wavelength dependence of the temperature and isotope effects is consistent with the model that different types of excitation occur on the low- and high-energy sides of the absorption band. The temperature and isotopic dependence of the low-energy side are consistent with its width being due to phonon interactions

  12. Pulse radiolysis study on temperature and pressure dependence of the yield of solvated electron in methanol from room temperature to supercritical condition

    International Nuclear Information System (INIS)

    Han, Zhenhui; He, Hui; Lin, Mingzhang; Muroya, Yusa; Katsumura, Yosuke

    2012-09-01

    A new concept of nuclear reactor, supercritical water-cooled reactor (SCWR), has been proposed, which is based on the success of the use of supercritical water (SCW) in fossil fuel power plants for more than three decades. This new concept reactor has advantages of higher thermal conversion efficiency, simplicity in structure, safety, etc, and it has been selected as one of the reactor concepts for the next generation nuclear reactor systems. In these reactors, the same as in boiling water reactors (BWR) and pressurized water reactors (PWR), water is used not only as a coolant but also as a moderator. It is very important to understand the behavior of the radiolysis products of water under the supercritical condition, since the water is exposed to a strong radiation field under very high temperature condition. Usually, in order to predict the concentrations of water decomposition products with carrying out some kinds of computer simulations, knowledge of the temperature and/or pressure dependent G-values (denoting the experimentally measured radiolytic yields) as well as of the rate constants of a set of reactions becomes very important. Therefore, in recent years, two groups from Argonne National Laboratory and The University of Tokyo, simultaneously conducted two projects aimed at obtaining basic data on radiolysis of SCW. However, it is still lack of reliable radiolytic yields of water decomposition products in very high temperature region. As we known, the properties of solvated electrons in polar liquid are very helpful for our understanding how they play a central role in many processes, such as solvation and reducing reactions. The solvated electron can also be used as a probe to determine the dynamic nature of the polar liquid systems. Comparing to water, the primary alcohols have much milder critical points, for example, for water and methanol, the critical temperature and pressure are 374 deg. C and 22.1 MPa and 239.5 deg. C and 8.1 MPa, respectively

  13. Plasma treatment for producing electron emitters

    Science.gov (United States)

    Coates, Don Mayo; Walter, Kevin Carl

    2001-01-01

    Plasma treatment for producing carbonaceous field emission electron emitters is disclosed. A plasma of ions is generated in a closed chamber and used to surround the exposed surface of a carbonaceous material. A voltage is applied to an electrode that is in contact with the carbonaceous material. This voltage has a negative potential relative to a second electrode in the chamber and serves to accelerate the ions toward the carbonaceous material and provide an ion energy sufficient to etch the exposed surface of the carbonaceous material but not sufficient to result in the implantation of the ions within the carbonaceous material. Preferably, the ions used are those of an inert gas or an inert gas with a small amount of added nitrogen.

  14. The EPR paradox, the hydrated (solvated) electron, and the reactions of the hydrated electron (Preprint no. RC-02)

    International Nuclear Information System (INIS)

    Gopinathan, C.

    1991-01-01

    Einstein, Podolsky and Rosen pointed out in 1935 a serious flaw in the reasoning behind quantum mechanical modelling. It is shown in this work that this flaw applies to the interpretation of the hydrated electron and its reactions as well. (author). 3 refs

  15. Microscopic solvation of a lithium atom in water-ammonia mixed clusters: solvent coordination and electron localization in presence of a counterion.

    Science.gov (United States)

    Pratihar, Subha; Chandra, Amalendu

    2008-07-14

    The microsolvation structures and energetics of water-ammonia mixed clusters containing a lithium atom, i.e., Li(H(2)O)(n)(NH(3)), n = 1-5, are investigated by means of ab initio theoretical calculations. Several structural aspects such as the solvent coordination to the metal ion and binding motifs of the free valence electron of the metal are investigated. We also study the energetics aspects such as the dependence of vertical ionization energies on the cluster size, and all these structural and energetics aspects are compared to the corresponding results of previously studied anionic water-ammonia clusters without a metal ion. It is found that the Li-O and Li-N interactions play a very important role in stabilizing the lithium-water-ammonia clusters, and the presence of these metal ion-solvent interactions also affect the characteristics of electron solvation in these clusters. This is seen from the spatial distribution of the singly occupied molecular orbital (SOMO) which holds the ejected valence electron of the Li atom. For very small clusters, SOMO electron density is found to exist mainly at the vicinity of the Li atom, whereas for larger clusters, it is distributed outside the first solvation shell. The free dangling hydrogens of water and ammonia molecules are involved in capturing the SOMO electron density. In some of the conformers, OH{e}HO and OH{e}HN types of interactions are found to be present. The presence of the metal ion at the center of the cluster ensures that the ejected electron is solvated at a surface state only, whereas both surface and interiorlike states were found for the free electron in the corresponding anionic clusters without a metal ion. The vertical ionization energies of the present clusters are found to be higher than the vertical detachment energies of the corresponding anionic clusters which signify a relatively stronger binding of the free electron in the presence of the positive metal counterion. The shifts in different

  16. Where do ions solvate?

    Indian Academy of Sciences (India)

    We study a simple model of ionic solvation inside a water cluster. The cluster is modeled as a spherical dielectric continuum. It is found that unpolarizable ions always prefer the bulk solvation. On the other hand, for polarizable ions, there exists a critical value of polarization above which surface solvation becomes ...

  17. STANFORD: Producing highly polarized electrons (2)

    International Nuclear Information System (INIS)

    Anon.

    1991-01-01

    Electron spin polarization above 70% by photoemission from a specially prepared semiconductor has been achieved by T. Maruyama and E. Garwin of the Stanford Linear Accelerator Center (SLAC), R. Prepost and G. Zapalac of Wisconsin, and J. Walker and S. Smith of Berkeley

  18. Electron acceleration using laser produced plasmas

    CERN Multimedia

    CERN. Geneva; Landua, Rolf

    2005-01-01

    Low density plasmas have long been of interest as a potential medium for particle acceleration since relativistic plasma waves are capable of supporting electric fields greater than 100 GeV/m. The physics of particle acceleration using plasmas will be reviewed, and new results will be discussed which have demonstrated that relatively narrow energy spread (<3%) beams having energies greater than 100 MeV can be produced from femtosecond laser plasma interactions. Future experiments and potential applications will also be discussed.

  19. Avoiding fractional electrons in subsystem DFT based ab-initio molecular dynamics yields accurate models for liquid water and solvated OH radical.

    Science.gov (United States)

    Genova, Alessandro; Ceresoli, Davide; Pavanello, Michele

    2016-06-21

    In this work we achieve three milestones: (1) we present a subsystem DFT method capable of running ab-initio molecular dynamics simulations accurately and efficiently. (2) In order to rid the simulations of inter-molecular self-interaction error, we exploit the ability of semilocal frozen density embedding formulation of subsystem DFT to represent the total electron density as a sum of localized subsystem electron densities that are constrained to integrate to a preset, constant number of electrons; the success of the method relies on the fact that employed semilocal nonadditive kinetic energy functionals effectively cancel out errors in semilocal exchange-correlation potentials that are linked to static correlation effects and self-interaction. (3) We demonstrate this concept by simulating liquid water and solvated OH(•) radical. While the bulk of our simulations have been performed on a periodic box containing 64 independent water molecules for 52 ps, we also simulated a box containing 256 water molecules for 22 ps. The results show that, provided one employs an accurate nonadditive kinetic energy functional, the dynamics of liquid water and OH(•) radical are in semiquantitative agreement with experimental results or higher-level electronic structure calculations. Our assessments are based upon comparisons of radial and angular distribution functions as well as the diffusion coefficient of the liquid.

  20. Avoiding fractional electrons in subsystem DFT based ab-initio molecular dynamics yields accurate models for liquid water and solvated OH radical

    International Nuclear Information System (INIS)

    Genova, Alessandro; Pavanello, Michele; Ceresoli, Davide

    2016-01-01

    In this work we achieve three milestones: (1) we present a subsystem DFT method capable of running ab-initio molecular dynamics simulations accurately and efficiently. (2) In order to rid the simulations of inter-molecular self-interaction error, we exploit the ability of semilocal frozen density embedding formulation of subsystem DFT to represent the total electron density as a sum of localized subsystem electron densities that are constrained to integrate to a preset, constant number of electrons; the success of the method relies on the fact that employed semilocal nonadditive kinetic energy functionals effectively cancel out errors in semilocal exchange–correlation potentials that are linked to static correlation effects and self-interaction. (3) We demonstrate this concept by simulating liquid water and solvated OH • radical. While the bulk of our simulations have been performed on a periodic box containing 64 independent water molecules for 52 ps, we also simulated a box containing 256 water molecules for 22 ps. The results show that, provided one employs an accurate nonadditive kinetic energy functional, the dynamics of liquid water and OH • radical are in semiquantitative agreement with experimental results or higher-level electronic structure calculations. Our assessments are based upon comparisons of radial and angular distribution functions as well as the diffusion coefficient of the liquid.

  1. Quantitative structure-retention relationship studies using immobilized artificial membrane chromatography I: amended linear solvation energy relationships with the introduction of a molecular electronic factor.

    Science.gov (United States)

    Li, Jie; Sun, Jin; Cui, Shengmiao; He, Zhonggui

    2006-11-03

    Linear solvation energy relationships (LSERs) amended by the introduction of a molecular electronic factor were employed to establish quantitative structure-retention relationships using immobilized artificial membrane (IAM) chromatography, in particular ionizable solutes. The chromatographic indices, log k(IAM), were determined by HPLC on an IAM.PC.DD2 column for 53 structurally diverse compounds, including neutral, acidic and basic compounds. Unlike neutral compounds, the IAM chromatographic retention of ionizable compounds was affected by their molecular charge state. When the mean net charge per molecule (delta) was introduced into the amended LSER as the sixth variable, the LSER regression coefficient was significantly improved for the test set including ionizable solutes. The delta coefficients of acidic and basic compounds were quite different indicating that the molecular electronic factor had a markedly different impact on the retention of acidic and basic compounds on IAM column. Ionization of acidic compounds containing a carboxylic group tended to impair their retention on IAM, while the ionization of basic compounds did not have such a marked effect. In addition, the extra-interaction with the polar head of phospholipids might cause a certain change in the retention of basic compounds. A comparison of calculated and experimental retention indices suggested that the semi-empirical LSER amended by the addition of a molecular electronic factor was able to reproduce adequately the experimental retention factors of the structurally diverse solutes investigated.

  2. The scavenging of the precursors of the solvated electrons fom the positron lifetime spectroscopy and the Doppler broadening of annihilation line shape technique

    International Nuclear Information System (INIS)

    Abbe, J.C.; Duplatre, G.; Maddock, A.G.; Haessler, A.

    1979-01-01

    The electron scavenging properties in water of two series of solutes are investigated, using the positron as a probe. For a better interpretation of the data, both the lifetime specroscopy and the Doppler broadening of annihilation line shape technique are used. All solutes inhibit the positronium (Ps) formation, by the scavenging of electron. The first series consists of the halate ions, that should follow the Hunt linear relation between the rate constant for reaction with the solvated electrons, ksub(e - sub(aq)+S) and that for its precursors(s), 1/C 37 . The Ps inhibition constants, k, are 0.14, 1.44 and 3.45M -1 for ClO 3 - , BrO 3 - and IO 3 - respectively. This sequence is quantitatively consistent with that of the respective ksub(e - sub(aq)+S). The second series includes the SeO 4 -- , Te(OH) 6 and BrO 4 - species, and the Ps inhibition constants are 5.62, 10.5 and 14.3 respectively. Theses values are much higher than expected from the ksub(e - sub(aq)+S) constants, on basis of the Hunt relation, in agreement with previous results from pulse radiolysis experiments

  3. Ion-Ion Plasmas Produced by Electron Beams

    Science.gov (United States)

    Fernsler, R. F.; Leonhardt, D.; Walton, S. G.; Meger, R. A.

    2001-10-01

    The ability of plasmas to etch deep, small-scale features in materials is limited by localized charging of the features. The features charge because of the difference in electron and ion anisotropy, and thus one solution now being explored is to use ion-ion plasmas in place of electron-ion plasmas. Ion-ion plasmas are effectively electron-free and consist mainly of positive and negative ions. Since the two ion species behave similarly, localized charging is largely eliminated. However, the only way to produce ion-ion plasmas at low gas pressure is to convert electrons into negative ions through two-body attachment to neutrals. While the electron attachment rate is large at low electron temperatures (Te < 1 eV) in many of the halogen gases used for processing, these temperatures occur in most reactors only during the afterglow when the heating fields are turned off and the plasma is decaying. By contrast, Te is low nearly all the time in plasmas produced by electron beams, and therefore electron beams can potentially produce ion-ion plasmas continuously. The theory of ion-ion plasmas formed by pulsed electron beams is examined in this talk and compared with experimental results presented elsewhere [1]. Some general limitations of ion-ion plasmas, including relatively low flux levels, are discussed as well. [1] See the presentation by D. Leonhardt et al. at this conference.

  4. Energy Spread Reduction of Electron Beams Produced via Laser Wake

    Energy Technology Data Exchange (ETDEWEB)

    Pollock, Bradley Bolt [Univ. of California, San Diego, CA (United States)

    2012-01-01

    Laser wakefield acceleration of electrons holds great promise for producing ultra-compact stages of GeV scale, high quality electron beams for applications such as x-ray free electron lasers and high energy colliders. Ultra-high intensity laser pulses can be self-guided by relativistic plasma waves over tens of vacuum diffraction lengths, to give >1 GeV energy in cm-scale low density plasma using ionization-induced injection to inject charge into the wake at low densities. This thesis describes a series of experiments which investigates the physics of LWFA in the self-guided blowout regime. Beginning with high density gas jet experiments the scaling of the LWFA-produced electron beam energy with plasma electron density is found to be in excellent agreement with both phenomenological theory and with 3-D PIC simulations. It is also determined that self-trapping of background electrons into the wake exhibits a threshold as a function of the electron density, and at the densities required to produce electron beams with energies exceeding 1 GeV a different mechanism is required to trap charge into low density wakes. By introducing small concentrations of high-Z gas to the nominal He background the ionization-induced injection mechanism is enabled. Electron trapping is observed at densities as low as 1.3 x 1018 cm-3 in a gas cell target, and 1.45 GeV electrons are demonstrated for the first time from LWFA. This is currently the highest electron energy ever produced from LWFA. The ionization-induced trapping mechanism is also shown to generate quasi-continuous electron beam energies, which is undesirable for accelerator applications. By limiting the region over which ionization-induced trapping occurs, the energy spread of the electron beams can be controlled. The development of a novel two-stage gas cell target provides the capability to tailor the gas composition in the longitudinal direction, and confine the trapping process to occur only in a

  5. Ionic liquids: radiation chemistry, solvation dynamics and reactivity patterns

    International Nuclear Information System (INIS)

    Wishart, J.F.; Funston, A.M.; Szreder, T.

    2006-01-01

    Ionic liquids (ILs) are a rapidly expanding family of condensed-phase media with important applications in energy production, nuclear fuel and waste processing, improving the efficiency and safety of industrial chemical processes, and pollution prevention. ILs are nonvolatile, noncombustible, highly conductive, recyclable and capable of dissolving a wide variety of materials. They are finding new uses in chemical synthesis, catalysis, separations chemistry, electrochemistry and other areas. Ionic liquids have dramatically different properties compared to conventional molecular solvents, and they provide a new and unusual environment to test our theoretical understanding of charge transfer and other reactions. We are interested in how IL properties influence physical and dynamical processes that determine the stability and lifetimes of reactive intermediates and thereby affect the courses of chemical reactions and product distributions. Successful use of ionic liquids in radiation-filled environments, where their safety advantages could be significant, requires an understanding of ionic liquid radiation chemistry. For example, characterizing the primary steps of IL radiolysis will reveal radiolytic degradation pathways and suggest ways to prevent them or mitigate their effects on the properties of the material. An understanding of ionic liquid radiation chemistry will also facilitate pulse radiolysis studies of general chemical reactivity in ILs, which will aid in the development of energy production, chemical industry and environmental applications. Pulse radiolysis of [R 4 N][NTf 2 ] [R 4 N][N(CN) 2 ], and [R 4 P][N(CN) 2 ] ionic liquids produces solvated electrons that absorb over a broad range in the near infrared and persisting for hundreds of nanoseconds. Systematic cation variation shows that solvated electron's spectroscopic properties depend strongly on the lattice structure of the ionic liquid. Very early in our radiolysis studies it became evident that

  6. A Non-Exploding Alkali Metal Drop on Water: From Blue Solvated Electrons to Bursting Molten Hydroxide

    Czech Academy of Sciences Publication Activity Database

    Mason, Philip E.; Buttersack, T.; Bauerecker, S.; Jungwirth, Pavel

    2016-01-01

    Roč. 55, č. 42 (2016), s. 13019-13022 ISSN 1433-7851 R&D Projects: GA ČR(CZ) GBP208/12/G016 Institutional support: RVO:61388963 Keywords : sodium potassium alloy * water * hydrated electrons Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 11.994, year: 2016

  7. Electron beam processing of fresh produce - A critical review

    Science.gov (United States)

    Pillai, Suresh D.; Shayanfar, Shima

    2018-02-01

    To meet the increasing global demand for fresh produce, robust processing methods that ensures both the safety and quality of fresh produce are needed. Since fresh produce cannot withstand thermal processing conditions, most of common safety interventions used in other foods are ineffective. Electron beam (eBeam) is a non-thermal technology that can be used to extend the shelf life and ensure the microbiological safety of fresh produce. There have been studies documenting the application of eBeam to ensure both safety and quality in fresh produce, however, there are still unexplored areas that still need further research. This is a critical review on the current literature on the application of eBeam technology for fresh produce.

  8. Electron-Beam Produced Air Plasma: Optical and Electrical Diagnostics

    Science.gov (United States)

    Vidmar, Robert; Stalder, Kenneth; Seeley, Megan

    2006-10-01

    High energy electron impact excitation is used to stimulate optical emissions that quantify the measurement of electron beam current. A 100 keV 10-ma electron beam source is used to produce air plasma in a test cell at a pressure between 1 mTorr and 760 Torr. Optical emissions originating from the N2 2^nd positive line at 337.1 nm and the N2^+ 1^st negative line at 391.4 nm are observed. Details on calibration using signals from an isolated transmission window and a Faraday plate are discussed. Results using this technique and other electrical signal are presented.

  9. Evolution of the spectrum of the solvated electron in BeF2 aqueous glasses at 76 K

    International Nuclear Information System (INIS)

    Nguyen, T.Q.; Walker, D.C.; Gillis, H.A.

    1978-01-01

    Evidence is presented for a spontaneous shift from infrared-to- red-to-green in the overall spectrum of the electron trapped in an aqueous glass at 76 K following nanosecond pulse radiolysis. As with the alcohols, after the pulse the infrared absorption decays, there is a growth-then-decay of absorbance at intermediate wavelengths and net growth of absorption due to the equilibrated trapped electron state, e - /sub vis/. This progressive transition was not characterised by a single-step process and was discernible in aqueous glasses containing 7.5 or 10.7M BeF 2 in D 2 O. At higher BeF 2 concentrations, or with LiBr as glass-forming electrolyte, no growth of e - /sub vis/ was observed, probably because of concurrent loss of e - /sub vis/ in those glasses, as in LiCl and other glasses. BeF 2 glasses of trapped electrons showed several other features of interest: (i) wavelength- selective bleaching of the e - /sub vis/ band indicates that it is composed of a broad ''green'' band (lambda/sub max/, 530--590 nm) which bleaches homogeneously, and a broad ''red'' region which bleaches inhomogeneously. (ii) lambda/sub max/ for e - /sub vis/ changes with BeF 2 concentration, being blue shifted with increasing concentration , with both green and red underlying structures shifting slightly. (iii) No absorption due to F - 2 was found following pulse radiolysis in these glasses at 76 K. (iv) Several recent findings with LiCl are mimicked by F - 2 glasses. For instance, G (e - /sub vis/) increases and G (e - /sub ir/) decreases as the electrolyte concentration is increased, while the combined yield remains constant at 1.8 +- 0.1

  10. NREL Scientists Report First Solar Cell Producing More Electrons In

    Science.gov (United States)

    measured in operating quantum dot solar cells at low light intensity; these cells showed significant power Photocurrent Than Solar Photons Entering Cell | News | NREL NREL Scientists Report First Solar Cell Producing More Electrons In Photocurrent Than Solar Photons Entering Cell News Release: NREL

  11. Femtosecond Soft X-ray Spectroscopy of Solvated Transition-Metal Complexes: Deciphering the Interplay of Electronic and Structural Dynamics

    Energy Technology Data Exchange (ETDEWEB)

    Huse, Nils; Cho, Hana; Hong, Kiryong; Jamula, Lindsey; de Groot, Frank M. F.; Kim, Tae Kyu; McCusker, James K.; Schoenlein, Robert W.

    2011-04-21

    We present the first implementation of femtosecond soft X-ray spectroscopy as an ultrafast direct probe of the excited-state valence orbitals in solution-phase molecules. This method is applied to photoinduced spin crossover of [Fe(tren(py)3)]2+, where the ultrafast spinstate conversion of the metal ion, initiated by metal-to-ligand charge-transfer excitation, is directly measured using the intrinsic spin-state selectivity of the soft X-ray L-edge transitions. Our results provide important experimental data concerning the mechanism of ultrafast spin-state conversion and subsequent electronic and structural dynamics, highlighting the potential of this technique to study ultrafast phenomena in the solution phase.

  12. Intense pulsed sources of ions and electrons produced by lasers

    International Nuclear Information System (INIS)

    Bourrabier, G.; Consoli, T.; Slama, L.

    1966-11-01

    We describe a device for the acceleration of the plasma burst produced by focusing a laser beam into a metal target. We extract the electrons and the ions from the plasma. The maximum current is around 2000 amperes during few microseconds. The study of the effect of the kind of the target on the characteristics of the current shows the great importance of the initial conditions that is the ionisation potential of the target and the energy laser. (authors) [fr

  13. [Experimental and computation studies of polar solvation

    International Nuclear Information System (INIS)

    1990-01-01

    This report from the Pennsylvania State University contains seven sections: (1) radiative rate effects in solvatlvatochromic probes; (2) intramolecular charge transfer reactions; (3) Solvation dynamics in low temperature alcohols; (4) Ionic solvation dynamics; (5) solvation and proton-transfer dynamics in 7-azaindole; (6) computer simulations of solvation dynamics; (7) solvation in supercritical fluids. 20 refs., 11 figs

  14. Comparison of the secondary electrons produced by proton and electron beams in water

    Energy Technology Data Exchange (ETDEWEB)

    Kia, Mohammad Reza, E-mail: m-r-kia@aut.ac.ir; Noshad, Houshyar [Department of Energy Engineering and Physics, Amirkabir University of Technology (Tehran Polytechnic), P.O. Box 15875-4413, Hafez Avenue, Tehran (Iran, Islamic Republic of)

    2016-05-15

    The secondary electrons produced in water by electron and proton beams are compared with each other. The total ionization cross section (TICS) for an electron impact in water is obtained by using the binary-encounter-Bethe model. Hence, an empirical equation based on two adjustable fitting parameters is presented to determine the TICS for proton impact in media. In order to calculate the projectile trajectory, a set of stochastic differential equations based on the inelastic collision, elastic scattering, and bremsstrahlung emission are used. In accordance with the projectile trajectory, the depth dose deposition, electron energy loss distribution in a certain depth, and secondary electrons produced in water are calculated. The obtained results for the depth dose deposition and energy loss distribution in certain depth for electron and proton beams with various incident energies in media are in excellent agreement with the reported experimental data. The difference between the profiles for the depth dose deposition and production of secondary electrons for a proton beam can be ignored approximately. But, these profiles for an electron beam are completely different due to the effect of elastic scattering on electron trajectory.

  15. Electronic emission produced by light projectiles at intermediate energies

    International Nuclear Information System (INIS)

    Bernardi, G.C.

    1989-01-01

    Two aspects of the electronic emission produced by light projectiles of intermediate energies have been studied experimentally. In the first place, measurements of angular distributions in the range from θ = 0 deg -50 deg induced by collisions of 50-200 keV H + incident on He have been realized. It was found that the double differential cross section of electron emission presents a structure focussed in the forward direction and which extends up to relatively large angles. Secondly, the dependence of the double differential cross section on the projectile charge was studied using H + and He 3 2+ projectiles of 50 and 100 keV/amu incident on He. Strong deviations from a constant scaling factor were found for increasing projectile charge. The double differential cross sections and the single differential cross sections as a function of the emission angle, and the ratios of the emissions induced by He 3 2+ and H + at equal incident projectile velocities are compared with the 'Continuum Distorted Wave-Eikonal Initial State' (CDW-EIS) approximation and the 'Classical Trajectory Monte Carlo' (CTMC) method. Both approximations, in which the potential of the projectile exercises a relevant role, reproduce the general aspects of the experimental results. An electron analyzer and the corresponding projectile beam line has been designed and installed; it is characterized by a series of properties which are particularly appropriate for the study of double differential electronic emission in gaseous as well as solid targets. The design permits to assure the conditions to obtain a well localized gaseous target and avoid instrumental distortions of the measured distributions. (Author) [es

  16. Proton solvation and proton transfer in chemical and electrochemical processes

    International Nuclear Information System (INIS)

    Lengyel, S.; Conway, B.E.

    1983-01-01

    This chapter examines the proton solvation and characterization of the H 3 O + ion, proton transfer in chemical ionization processes in solution, continuous proton transfer in conductance processes, and proton transfer in electrode processes. Topics considered include the condition of the proton in solution, the molecular structure of the H 3 O + ion, thermodynamics of proton solvation, overall hydration energy of the proton, hydration of H 3 O + , deuteron solvation, partial molal entropy and volume and the entropy of proton hydration, proton solvation in alcoholic solutions, analogies to electrons in semiconductors, continuous proton transfer in conductance, definition and phenomenology of the unusual mobility of the proton in solution, solvent structure changes in relation to anomalous proton mobility, the kinetics of the proton-transfer event, theories of abnormal proton conductance, and the general theory of the contribution of transfer reactions to overall transport processes

  17. Atmospheric nitrous oxide produced by solar protons and relativistic electrons

    International Nuclear Information System (INIS)

    Prasad, S.S.; Zipf, E.C.

    1981-01-01

    An alternative means of nitric oxide production in the stratosphere to that of direct formation in the upper atmosphere by solar proton (SP) events and by relativistic electron precipitation (REP) events from the Earth's radiation belt, is described. It is suggested that nitrous oxide is produced in the mesosphere and then migrates downward and is converted in the stratosphere to NO by the reaction N 2 O + O( 1 D) → 2 NO. Such a process could amplify the direct NO production by >10%. Mesospheric nitrous oxide mixing ratios increase to values as high as 6 x 10 -7 due to REP- and SP- related production. Lateral transport will reduce these high values but mesospheric mixing ratios of N 2 O in the high latitudes would approach 10 -7 , considerably greater than those expected on the basis of theories which neglect REP- and SP-related production of this species. (U.K.)

  18. Test of models for electron transport in laser produced plasmas

    International Nuclear Information System (INIS)

    Colombant, D.G.; Manheimer, W.M.; Busquet, M.

    2005-01-01

    This paper examines five different models of electron thermal transport in laser produced spherical implosions. These are classical, classical with a flux limit f, delocalization, beam deposition model, and Fokker-Planck solutions. In small targets, the results are strongly dependent on f for flux limit models, with small f's generating very steep temperature gradients. Delocalization models are characterized by large preheat in the center of the target. The beam deposition model agrees reasonably well with the Fokker-Planck simulation results. For large, high gain fusion targets, the delocalization model shows the gain substantially reduced by the preheat. However, flux limitation models show gain largely independent of f, with the beam deposition model also showing the same high gain

  19. Process for producing a coating composition. [electron beam irradiation

    Energy Technology Data Exchange (ETDEWEB)

    Kimura, T; Harada, H; Kobayashi, S; Nakamoto, H; Sunano, K

    1968-07-19

    An easily hardenable acrylic coating composition is produced by irradiation with low energy electron beams to economize the industrial application of the composition. A polymer with molecular weights in the 5,000 to 500,000 range is composed of 1 to 40% by weight of a vinyl monomer containing a glycidyl radical, 30 to 99% of a methacrylic monomer and 0 to 69% of other copolymerizable vinyl monomers. This polymer dissolves in a monomer containing at least 30% of an acrylic monomer and 70% of other vinyl monomers. The reaction takes place between 0.1 to 1.0 mole of vinyl monomer containing a carboxyl radical and one mole of glycidyl radical in the solution. In an embodiment, 17.5% by weight of glycidyl methacrylate and 82.5% of alkyl acrylate are polymerized in suspension in the presence of a catalyst to form a bead like polymer with molecular weights in the 5,000 to 500,000 range. After 120 parts of the bead like polymer are dissolved in 180 parts of the acrylic monomer in the presence of a polymerization inhibitor by heating, 22 parts of ..cap alpha.., ..beta..- unsaturated monocarboxylic acid are added to the solution to react with the glycidyl radical, whereby a non-solvent type coating material containing the polymer having a vinyl radical side chain is produced. In the place of the catalyst, electron beams can be used at an energy level of 0.1 to 20 MeV. The dose rate may be in the range of 0.1 to 2.0 Mrad/sec.

  20. Standard electrode potential, Tafel equation, and the solvation thermodynamics.

    Science.gov (United States)

    Matyushov, Dmitry V

    2009-06-21

    Equilibrium in the electronic subsystem across the solution-metal interface is considered to connect the standard electrode potential to the statistics of localized electronic states in solution. We argue that a correct derivation of the Nernst equation for the electrode potential requires a careful separation of the relevant time scales. An equation for the standard metal potential is derived linking it to the thermodynamics of solvation. The Anderson-Newns model for electronic delocalization between the solution and the electrode is combined with a bilinear model of solute-solvent coupling introducing nonlinear solvation into the theory of heterogeneous electron transfer. We therefore are capable of addressing the question of how nonlinear solvation affects electrochemical observables. The transfer coefficient of electrode kinetics is shown to be equal to the derivative of the free energy, or generalized force, required to shift the unoccupied electronic level in the bulk. The transfer coefficient thus directly quantifies the extent of nonlinear solvation of the redox couple. The current model allows the transfer coefficient to deviate from the value of 0.5 of the linear solvation models at zero electrode overpotential. The electrode current curves become asymmetric in respect to the change in the sign of the electrode overpotential.

  1. Process for producing a novel copolymer. [electron beams

    Energy Technology Data Exchange (ETDEWEB)

    Oiwa, M; Matsumoto, A; Tojima, M; Matsumoto, K; Sasaki, H

    1970-11-27

    Diaryl oxalate present in a polymer not only decomposes at lower temperatures, but also provides for stronger free radicals initiating polymerization than diaryl oxalate present in a monomer. A copolymer of vinyl monomers is produced by providing a diaryl oxalate polymer or a diaryl oxalate monomer-co-vinyl monomer, decomposing them to release the diaryl oxalate units by heating or irradiating with radiation thereby copolymerizing the vinyl monomer with the polymer radicals by utilizing the diaryl oxalate unit. For example, a single diaryl oxalate polymer or a copolymer containing the diaryl oxalate polymer as a constituent of the copolymer are irradiated or heated with a vinyl monomer, i.e. methyl methacrylate, acrylnitrile, vinyl acetate, styrene etc., to form a copolymer without difficulty. In one of the examples, 500 g of diaryl oxalate monomer, 1,200 ml of benzene and 0.2 mol/l of benzoil peroxide as an initiator were mixed and polymerized in nitrogen gas at 70/sup 0/C for 8 hrs. From this polymerized solution, a polymer was deposited in methanol. The produced polymer had an iodin value of 77.7 with a yield of 35%. The gel content of the produced polymer was 98.9% for 10 Mrad. This polymer was dissolved in methyl methacrylate, thereafter filled in a mold and irradiated with electron beams of 2 MeV in nitrogen gas to harden it. The advantage of this process is that the polymerization is effected with low energy radiations at room temperature without requiring any catalyst.

  2. Interfacial solvation thermodynamics

    International Nuclear Information System (INIS)

    Ben-Amotz, Dor

    2016-01-01

    Previous studies have reached conflicting conclusions regarding the interplay of cavity formation, polarizability, desolvation, and surface capillary waves in driving the interfacial adsorptions of ions and molecules at air–water interfaces. Here we revisit these questions by combining exact potential distribution results with linear response theory and other physically motivated approximations. The results highlight both exact and approximate compensation relations pertaining to direct (solute–solvent) and indirect (solvent–solvent) contributions to adsorption thermodynamics, of relevance to solvation at air–water interfaces, as well as a broader class of processes linked to the mean force potential between ions, molecules, nanoparticles, proteins, and biological assemblies. (paper)

  3. Fragmentation of cluster ions produced by electron impact ionization

    International Nuclear Information System (INIS)

    Parajuli, R.

    2001-12-01

    By studying fragmentation of dimer and cluster ions produced by electron impact ionization of a neutral cluster beam, it is possible to elucidate structure, stability and energetics of these species and the dynamics of the corresponding decay reactions. Fragmentation of carbon cluster ions formed from C 6 0 fullerenes, rare gas cluster ions and dimer ions and simple molecular cluster ions (oxygen and nitrogen) and dimer ions have been studied in this thesis using a high resolution two sector field mass spectrometer of reversed geometry and a NIER type electron impact ion source. Spontaneous decay reactions of triply and quadruply charged C 4 0 z + and C 4 1 z + cluster ions which are formed from C 6 0 fullerenes by electron impact ionization have been analyzed. A new but very weak decay reaction for the even-sized carbon clusters ions is observed, namely loss of C 3 . The odd-sized clusters ions preferentially decay by loss of carbon atoms and, to a lesser degree, trimers. A weak signal due to C 2 loss is observed for C 4 1 3 + ion. These decay channels are discussed in terms of the geometric structure of these metastable, relatively cold cluster ions. Measurements on metastable fragmentation of mass selected rare gas cluster ions (Ne, Ar, Kr) which are produced by electron impact ionization of a neutral rare gas cluster beam have been carried out. From the shape of the fragment ion peaks (MIKE scan technique) information about the distribution of kinetic energy that is released in the decay reaction can be deduced. In this study, the peak shape observed for cluster ions with sizes larger than five is Gaussian and thus from the peak width the mean kinetic energy release of the corresponding decay reactions can be calculated. Using finite heat bath theory, the binding energies of the decaying cluster ions are calculated from these data and have been compared to data in the literature where available. In addition to the decay reactions of cluster ions the metastable

  4. Ultra-fast pulse radiolysis: A review of the recent system progress and its application to study on initial yields and solvation processes of solvated electrons in various kinds of alcohols

    International Nuclear Information System (INIS)

    Muroya, Yusa; Lin Mingzhang; Han Zhenhui; Kumagai, Yuta; Sakumi, Akira; Ueda, Toru; Katsumura, Yosuke

    2008-01-01

    In order to study radiation-induced fast phenomena, a new pulse radiolysis system with higher time resolution based on pulse-and-probe method was developed and utilized for practical work. A few picosecond electron beam generated from a linear accelerator, in which a laser photocathode RF-gun is introduced, was synchronized with a femtosecond laser pulse which is employed as the analyzing light. The synchronization precision between them was suppressed within 1.6 ps (rms). Converting the fundamental laser into white light continuum or optical parametric amplification allows to measure in the wide wavelength from visible to infrared region

  5. Shack-Hartmann Electron Densitometer (SHED): An Optical System for Diagnosing Free Electron Density in Laser-Produced Plasmas

    Science.gov (United States)

    2016-11-01

    Free Electron Density in Laser-Produced Plasmas by Anthony R Valenzuela Approved for public release; distribution is...AND SUBTITLE Shack-Hartmann Electron Densitometer (SHED): An Optical System for Diagnosing Free Electron Density in Laser-Produced Plasmas 5a...SUPPLEMENTARY NOTES 14. ABSTRACT The Shack-Hartmann Electron Densitometer is a novel method to diagnose ultrashort pulse laser–produced plasmas

  6. Electronic properties of interfaces produced by silicon wafer hydrophilic bonding

    Energy Technology Data Exchange (ETDEWEB)

    Trushin, Maxim

    2011-07-15

    The thesis presents the results of the investigations of electronic properties and defect states of dislocation networks (DNs) in silicon produced by wafers direct bonding technique. A new insight into the understanding of their very attractive properties was succeeded due to the usage of a new, recently developed silicon wafer direct bonding technique, allowing to create regular dislocation networks with predefined dislocation types and densities. Samples for the investigations were prepared by hydrophilic bonding of p-type Si (100) wafers with same small misorientation tilt angle ({proportional_to}0.5 ), but with four different twist misorientation angles Atw (being of < , 3 , 6 and 30 , respectively), thus giving rise to the different DN microstructure on every particular sample. The main experimental approach of this work was the measurements of current and capacitance of Schottky diodes prepared on the samples which contained the dislocation network at a depth that allowed one to realize all capabilities of different methods of space charge region spectroscopy (such as CV/IV, DLTS, ITS, etc.). The key tasks for the investigations were specified as the exploration of the DN-related gap states, their variations with gradually increasing twist angle Atw, investigation of the electrical field impact on the carrier emission from the dislocation-related states, as well as the establishing of the correlation between the electrical (DLTS), optical (photoluminescence PL) and structural (TEM) properties of DNs. The most important conclusions drawn from the experimental investigations and theoretical calculations can be formulated as follows: - DLTS measurements have revealed a great difference in the electronic structure of small-angle (SA) and large-angle (LA) bonded interfaces: dominating shallow level and a set of 6-7 deep levels were found in SA-samples with Atw of 1 and 3 , whereas the prevalent deep levels - in LA-samples with Atw of 6 and 30 . The critical twist

  7. Modifications of poly (vinilydene fluoride) under electronic excitations produced by charged particles (heavy ions and electrons)

    International Nuclear Information System (INIS)

    Fina, A.

    1990-04-01

    Some of the physico-chemical properties of organic solids like conductivity or permeation can be improved by irradiation. The aim of this work is to characterize modifications induced in poly (vinylidene fluoride) films (PVDF) by charged particles (ions and electrons), with electronic stopping power, for doses ranging from zero to twenty G-Grays. Influence of dose, density of electronic excitations, and flux (in particles per square centimeter), and the nature of defects induced by the beam, were studied with two methods: X-ray Photoelectron Spectroscopy (or XPS) for surface analysis, and electron Spin Resonance (or ESR) to probe the bulk of the film. Three ranges of doses are revealed in view of experimental results. At lower doses, PVDF undergoes deshydrofluorination induced by desorption; it is a low modifications regime. For intermediate range doses, conjugated carbon backbones of polyene compounds are produced. At higher doses, intermolecular interactions between the resulting fragments give a crosslinked network. For the upper limit of doses used, bond breaking results in a non reversible degradation of PVDF. In this last situation, direct atomic displacement of target atoms, is not negligible [fr

  8. Multiply excited molecules produced by photon and electron interactions

    International Nuclear Information System (INIS)

    Odagiri, T.; Kouchi, N.

    2006-01-01

    The photon and electron interactions with molecules resulting in the formation of multiply excited molecules and the subsequent decay are subjects of great interest because the independent electron model and Born-Oppenheimer approximation are much less reliable for the multiply excited states of molecules than for the ground and lower excited electronic states. We have three methods to observe and investigate multiply excited molecules: 1) Measurements of the cross sections for the emission of fluorescence emitted by neutral fragments in the photoexcitation of molecules as a function of incident photon energy [1-3], 2) Measurements of the electron energy-loss spectra tagged with the fluorescence photons emitted by neutral fragments [4], 3) Measurements of the cross sections for generating a pair of photons in absorption of a single photon by a molecule as a function of incident photon energy [5-7]. Multiply excited states degenerate with ionization continua, which make a large contribution in the cross section curve involving ionization processes. The key point of our methods is hence that we measure cross sections free from ionization. The feature of multiply excited states is noticeable in such a cross section curve. Recently we have measured: i) the cross sections for the emission of the Lyman- fluorescence in the photoexcitation of CH 4 as a function of incident photon energy in the range 18-51 eV, ii) the electron energy-loss spectrum of CH 4 tagged with the Lyman-photons at 80 eV incident electron energy and 10 electron scattering angle in the range of the energy loss 20-45 eV, in order to understand the formation and decay of the doubly excited methane in photon and electron interactions. [8] The results are summarized in this paper and the simultaneous excitation of two electrons by electron interaction is compared with that by photon interaction in terms of the oscillator strength. (authors)

  9. New initiatives for producing high current electron accelerators

    International Nuclear Information System (INIS)

    Faehl, R.J.; Keinigs, R.K.; Pogue, E.W.

    1996-01-01

    New classes of compact electron accelerators able to deliver multi-kiloamperes of pulsed 10-50 MeV electron beams are being studied. One class is based upon rf linac technology with dielectric-filled cavities. For materials with ε/ε o >>1, the greatly increased energy storage permits high current operation. The second type is a high energy injected betatron. Circulating current limits scale as Β 2 γ 3

  10. Solvation in supercritical water

    International Nuclear Information System (INIS)

    Cochran, H.D.; Cummings, P.T.; Karaborni, S.

    1991-01-01

    The aim of this work is to determine the solvation structure in supercritical water composed with that in ambient water and in simple supercritical solvents. Molecular dynamics studies have been undertaken of systems that model ionic sodium and chloride, atomic argon, and molecular methanol in supercritical aqueous solutions using the simple point charge model of Berendsen for water. Because of the strong interactions between water and ions, ionic solutes are strongly attractive in supercritical water, forming large clusters of water molecules around each ion. Methanol is found to be a weakly-attractive solute in supercritical water. The cluster of excess water molecules surrounding a dissolved ion or polar molecule in supercritical aqueous solutions is comparable to the solvent clusters surrounding attractive solutes in simple supercritical fluids. Likewise, the deficit of water molecules surrounding a dissolved argon atom in supercritical aqueous solutions is comparable to that surrounding repulsive solutes in simple supercritical fluids. The number of hydrogen bonds per water molecule in supercritical water was found to be about one third the number in ambient water. The number of hydrogen bonds per water molecule surrounding a central particle in supercritical water was only mildly affected by the identify of the central particle--atom, molecule, or ion. These results should be helpful in developing a qualitative understanding of important processes that occur in supercritical water. 29 refs., 6 figs

  11. Transition and synchrotron radiation produced by electrons and particle discrimination

    International Nuclear Information System (INIS)

    Merkel, B.; Repellin, J.-P.; Sauvage, G.; Chollet, J.C.; Dialinas, M.; Gaillard, J.-M.; Hrisoho, A.; Jean, P.

    1976-01-01

    Transition radiation from a radiator of 650 lithium foils has been studied in a multiwire proportional chamber filled with a Xenon-CO 2 mixture for two experimental configurations. With the chamber immediately after the radiator, particle discrimination comparable to those reported in the litterature (90% efficiency for electrons, 10% for hadrons) have been observed. With magnetic bending between the radiator and the xenon chamber typical efficiencies of 87% for electrons and less than 0.4% for hadrons have been measured. The discrimination obtained is at least a factor 20 better than for the more conventional configuration. In the latter case, synchrotron radiation has also been observed

  12. Positron-electron pairs produced in heavy-ion collisions

    International Nuclear Information System (INIS)

    Ahmad, I.; Austin, Sam. M.; Back, B. B.; Betts, R. R.; Calaprice, F. P.; Chan, K. C.; Chishti, A.; Conner, C. M.; Dunford, R. W.; Fox, J. D.

    1999-01-01

    The production of positron-electron pairs in collisions of 238 U+ 232 Th at 5.95 MeV/nucleon, and of 238 U+ 181 Ta at 5.95, 6.1, and 6.3 MeV/nucleon, has been studied with the APEX spectrometer at Argonne National Laboratory. Several analyses have been performed to search for sharp structures in sum-energy spectra for positron-electron pairs. Such features have been reported in previous experiments. No statistically convincing evidence for such behavior is observed in the present data. (c) 1999 The American Physical Society

  13. Characteristics of the fast electron emission produced during the ...

    Indian Academy of Sciences (India)

    water adsorption and other characteristics of the fast electron emission ..... that the surface charges which leak away when there is adosrbed water on ... implies that it is a measure of the supply of excited species rather than due to the charge.

  14. New particles produced in electron--positron annihilation

    International Nuclear Information System (INIS)

    Perl, M.L.

    1975-01-01

    The main properties of the new particles produced in e + e - annihilation are reviewed. Included are properties of the continuum region, the 4.1-GeV enhancement, the psi and psi', radiative decays of the psi and psi', singly charmed particle searches in e + - e - annihilation, and the e/sub μ/ events

  15. Electron acceleration by laser produced wake field: Pulse shape effect

    Science.gov (United States)

    Malik, Hitendra K.; Kumar, Sandeep; Nishida, Yasushi

    2007-12-01

    Analytical expressions are obtained for the longitudinal field (wake field: Ex), density perturbations ( ne') and the potential ( ϕ) behind a laser pulse propagating in a plasma with the pulse duration of the electron plasma period. A feasibility study on the wake field is carried out with Gaussian-like (GL) pulse, rectangular-triangular (RT) pulse and rectangular-Gaussian (RG) pulse considering one-dimensional weakly nonlinear theory ( ne'/n0≪1), and the maximum energy gain acquired by an electron is calculated for all these three types of the laser pulse shapes. A comparative study infers that the RT pulse yields the best results: In its case maximum electron energy gain is 33.5 MeV for a 30 fs pulse duration whereas in case of GL (RG) pulse of the same duration the gain is 28.6 (28.8)MeV at the laser frequency of 1.6 PHz and the intensity of 3.0 × 10 18 W/m 2. The field of the wake and hence the energy gain get enhanced for the higher laser frequency, larger pulse duration and higher laser intensity for all types of the pulses.

  16. Ionic Liquids: Radiation Chemistry, Solvation Dynamics and Reactivity Patterns

    International Nuclear Information System (INIS)

    Wishart, J.F.

    2011-01-01

    Ionic liquids (ILs) are a rapidly expanding family of condensed-phase media with important applications in energy production, nuclear fuel and waste processing, improving the efficiency and safety of industrial chemical processes, and pollution prevention. ILs generally have low volatilities and are combustion-resistant, highly conductive, recyclable and capable of dissolving a wide variety of materials. They are finding new uses in chemical synthesis, catalysis, separations chemistry, electrochemistry and other areas. Ionic liquids have dramatically different properties compared to conventional molecular solvents, and they provide a new and unusual environment to test our theoretical understanding of primary radiation chemistry, charge transfer and other reactions. We are interested in how IL properties influence physical and dynamical processes that determine the stability and lifetimes of reactive intermediates and thereby affect the courses of reactions and product distributions. We study these issues by characterization of primary radiolysis products and measurements of their yields and reactivity, quantification of electron solvation dynamics and scavenging of electrons in different states of solvation. From this knowledge we wish to learn how to predict radiolytic mechanisms and control them or mitigate their effects on the properties of materials used in nuclear fuel processing, for example, and to apply IL radiation chemistry to answer questions about general chemical reactivity in ionic liquids that will aid in the development of applications listed above. Very early in our radiolysis studies it became evident that the slow solvation dynamics of the excess electron in ILs (which vary over a wide viscosity range) increase the importance of pre-solvated electron reactivity and consequently alter product distributions and subsequent chemistry. This difference from conventional solvents has profound effects on predicting and controlling radiolytic yields

  17. Modeling nitrogen plasmas produced by intense electron beams

    Energy Technology Data Exchange (ETDEWEB)

    Angus, J. R.; Swanekamp, S. B.; Schumer, J. W.; Hinshelwood, D. D. [Plasma Physics Division, Naval Research Laboratory, Washington, DC 20375 (United States); Mosher, D.; Ottinger, P. F. [Independent contractors for NRL through Engility, Inc., Alexandria, Virginia 22314 (United States)

    2016-05-15

    A new gas–chemistry model is presented to treat the breakdown of a nitrogen gas with pressures on the order of 1 Torr from intense electron beams with current densities on the order of 10 kA/cm{sup 2} and pulse durations on the order of 100 ns. For these parameter regimes, the gas transitions from a weakly ionized molecular state to a strongly ionized atomic state on the time scale of the beam pulse. The model is coupled to a 0D–circuit model using the rigid–beam approximation that can be driven by specifying the time and spatial profiles of the beam pulse. Simulation results are in good agreement with experimental measurements of the line–integrated electron density from experiments done using the Gamble II generator at the Naval Research Laboratory. It is found that the species are mostly in the ground and metastable states during the atomic phase, but that ionization proceeds predominantly through thermal ionization of optically allowed states with excitation energies close to the ionization limit.

  18. Measurement of anomalous dimuons produced in electron-positron annihilations

    International Nuclear Information System (INIS)

    Seidman, K.M.

    1979-01-01

    An experimental search for anomalous events of the type μ + μ - + (missing energy and momentum) produced in e + e - annihilation at center-of-mass energies between 6.4 and 7.4 GeV is presented. Analysis of the data reveals 12 events, of which only 6 can be readily explained as background. It is concluded that anomalous dimuon events were found. Furthermore, these events are most simply interpreted as the production and subsequent decay of a pair of heavy leptons, tau +- , each with a mass of about 1.8 GeV/c 2 , and a muonic branching ratio, B(tau → ν/sub tau/μν/tau → all), = 0.21 +0 07 - 0 08 . Because the known family of leptons is so small, and because these leptons seem to be truly elementary particles, the discovery of new lepton is a major event in physics. This discovery can be viewed as a hint of a needed revision in the current paradigm of elementary particle physics. The historical, logical, and technological development of physics in progressing towards fields of increasingly abstract nature is noted. The experimental search, analysis, and interpretation presented here is considered an example of a model problem and solution within the current paradigm of high energy physics. This paradigm is not considered to be complete. On the basis of the Transcendental Meditation technique it is proposed that the systematic and precise exploration of consciousness and its relationship to physical matter is now feasible. It is proposed that the expansion of the current paradigm to include the pure consciousness state as a dynamical element in both the physical description of nature, and the experience of one's own inner nature is a necessity to accomplish the goal and fulfill the purpose of physics

  19. Characteristics of plasma in uranium atomic beam produced by electron-beam heating

    International Nuclear Information System (INIS)

    Ohba, Hironori; Shibata, Takemasa

    2000-08-01

    The electron temperature of plasma and the ion flux ratio in the uranium atomic beam produced by electron-beam heating were characterized with Langmuir probes. The electron temperature was 0.13 eV, which was lower than the evaporation surface temperature. The ion flux ratio to atomic beam flux was more than 3% at higher evaporation rates. The ion flux ratio has increased with decreasing acceleration energy of the electron-beam under constant electron-beam power. This is because of an increase of electron-beam current and a large ionization cross-section of uranium by electron-impact. It was confined that the plasma is produced by electron-impact ionization of the evaporated atoms at the evaporation source. (author)

  20. Direct measurement of macroscopic electric fields produced by collective effects in electron-impact experiments

    International Nuclear Information System (INIS)

    Velotta, R.; Avaldi, L.; Camilloni, R.; Giammanco, F.; Spinelli, N.; Stefani, G.

    1996-01-01

    The macroscopic electric field resulting from the space charge produced in electron-impact experiments has been characterized by using secondary electrons of well-defined energy (e.g., Auger or autoionizing electrons) as a probe. It is shown that the measurement of the kinetic-energy shifts suffered by secondary electrons is a suitable tool for the analysis of the self-generated electric field in a low-density plasma. copyright 1996 The American Physical Society

  1. Ion emission from laser-produced plasmas with two electron temperatures

    International Nuclear Information System (INIS)

    Wickens, L.M.; Allen, J.E.; Rumsby, P.T.

    1978-01-01

    An analytic theory for the expansion of a laser-produced plasma with two electron temperatures is presented. It is shown that from the ion-emission velocity spectrum such relevant parameters as the hot- to -cold-electron density ratio, the absolute hot- and cold-electron temperatures, and a sensitive measure of hot- and cold-electron temperature ratio can be deduced. A comparison with experimental results is presented

  2. X-Pol Potential: An Electronic Structure-Based Force Field for Molecular Dynamics Simulation of a Solvated Protein in Water.

    Science.gov (United States)

    Xie, Wangshen; Orozco, Modesto; Truhlar, Donald G; Gao, Jiali

    2009-02-17

    A recently proposed electronic structure-based force field called the explicit polarization (X-Pol) potential is used to study many-body electronic polarization effects in a protein, in particular by carrying out a molecular dynamics (MD) simulation of bovine pancreatic trypsin inhibitor (BPTI) in water with periodic boundary conditions. The primary unit cell is cubic with dimensions ~54 × 54 × 54 Å(3), and the total number of atoms in this cell is 14281. An approximate electronic wave function, consisting of 29026 basis functions for the entire system, is variationally optimized to give the minimum Born-Oppenheimer energy at every MD step; this allows the efficient evaluation of the required analytic forces for the dynamics. Intramolecular and intermolecular polarization and intramolecular charge transfer effects are examined and are found to be significant; for example, 17 out of 58 backbone carbonyls differ from neutrality on average by more than 0.1 electron, and the average charge on the six alanines varies from -0.05 to +0.09. The instantaneous excess charges vary even more widely; the backbone carbonyls have standard deviations in their fluctuating net charges from 0.03 to 0.05, and more than half of the residues have excess charges whose standard deviation exceeds 0.05. We conclude that the new-generation X-Pol force field permits the inclusion of time-dependent quantum mechanical polarization and charge transfer effects in much larger systems than was previously possible.

  3. Activation-energy for the reaction h+oh--]eaq- - kinetic determination of the enthalpy and entropy of solvation of the hydrated electron

    DEFF Research Database (Denmark)

    Hickle, B.; Sehested, Knud

    1985-01-01

    The reaction between atomic hydrogen and hydroxide ion in aqueous solutions H + OH- - eaq- + H20 has been studied by pulse radiolysis. The rate constant was measured at pH 11.7 and 12 by following the growth of the hydrated electron absorption at 600 nm. The activation energy of the reaction has...

  4. Formula for average energy required to produce a secondary electron in an insulator

    International Nuclear Information System (INIS)

    Xie Ai-Gen; Zhan Yu; Gao Zhi-Yong; Wu Hong-Yan

    2013-01-01

    Based on a simple classical model specifying that the primary electrons interact with the electrons of a lattice through the Coulomb force and a conclusion that the lattice scattering can be ignored, the formula for the average energy required to produce a secondary electron (in) is obtained. On the basis of the energy band of an insulator and the formula for in, the formula for the average energy required to produce a secondary electron in an insulator (in i ) is deduced as a function of the width of the forbidden band (E g ) and electron affinity χ. Experimental values and the in i values calculated with the formula are compared, and the results validate the theory that explains the relationships among E g , χ, and in i and suggest that the formula for in i is universal on the condition that the primary electrons at any energy hit the insulator. (condensed matter: electronic structure, electrical, magnetic, and optical properties)

  5. Calculation of X-ray emission produced by a quasi-monoenergetic electron distribution

    International Nuclear Information System (INIS)

    Fanaei, M.; Sadighi-Bonabi, R.

    2010-01-01

    Complete text of publication follows. By using an intense ultrafast laser interaction with plasma, generation of accelerated relativistic electrons with quasi monoenergetic spectrum has been possible. Analytic expressions for spectra and emission efficiencies of x-rays bremsstrahlung and characteristic line emission produced by a quasi-monoenergetic electron distribution from several targets are investigated. In this work, a Gaussian profile is assumed for the quasi-monoenergetic electron spectrum. The produced x-ray radiations are compared with the previous achieved results for a Maxwellian electron profile. These results and achievements are discussed in detail. Also, the outcomes can be evaluated with the experimental and simulated results.

  6. Electron beam producing system for very high acceleration voltages and beam powers

    International Nuclear Information System (INIS)

    Andelfinger, C.; Dommaschk, W.; Ott, W.; Ulrich, M.; Weber, G.

    1975-01-01

    An electron beam producing system for acceleration voltages on the order of megavolts and beam powers on the order of gigawatts is described. A tubular housing of insulating material is used, and adjacent to its one closed end, a field emission cathode with a large surface area is arranged, while at its other end, from which the electron beam emerges, an annular anode is arranged. The device for collimating the electron beam consists of annular electrodes. (auth)

  7. Hot electron effects on the satellite spectrum of laser-produced plasmas

    Energy Technology Data Exchange (ETDEWEB)

    Abdallah, J. [Los Alamos National Laboratory, PO Box 1663, Los Alamos, NM (United States); Faenov, A.Y.; Pikuz, T.A. [MISDC, NPO ' VNIIFTRI' , Mendeleevo, Moscow Region, 141570 (Russian Federation); Wilke, M.D.; Kyrala, G.A.; Clark, R.E.H. [Los Alamos National Laboratory, PO Box 1663, Los Alamos, NM (United States)

    1999-05-01

    In laser-produced plasmas, the interaction of the intense laser light with plasma electrons can produce high-energy superthermal electrons with energies in the keV range. These hot electrons can influence the level populations which determine spectral line structure. In the present paper, the effect of hot electrons on the X-ray satellite spectrum of laser-produced plasmas is studied. Calculated spectra are compared with experimental observations. Magnesium targets irradiated by three different types of laser pulses are considered. These include, a high-intensity 600 fs Nd-glass laser, a 1 ns Nd-glass laser, and a 2ns CO{sub 2} laser. The Nd-glass laser experiments were conducted recently at the Los Alamos Trident Facility and the CO{sub 2} data were recorded by MISDC. High-resolution spectra were measured near the He-like resonance line of magnesium. The calculations employ an electron energy distribution which includes a thermal and a hot electron component, as part of a detailed collisional-radiative model. Plasma parameters including electron temperature, density, and hot electron fraction are estimated by choosing best fits to the experimental measurements. The calculations show that hot electrons can cause several anomalous effects. The Li-like jkl, abcd, and qr satellites can show intensities which are generally attributed to electron densities in excess of 10{sup 23} cm{sup -3}. In addition, the relative amplitude of the intercombination line can be unusually large even at high electron densities due to enhanced collisional excitation of the 1s2p{sup 3}P state by hot electrons. (Copyright (c) 1999 Elsevier Science B.V., Amsterdam. All rights reserved.)

  8. Solvated Positron Chemistry. II

    DEFF Research Database (Denmark)

    Mogensen, O. E.

    1979-01-01

    The reaction of the hydrated positron, eaq+ with Cl−, Br−, and I− ions in aqueous solutions was studied by means of positron The measured angular correlation curves for [Cl−, e+], [Br−, e+, and [I−, e+] bound states were in good agreement with th Because of this agreement and the fact...... that the calculated positron wavefunctions penetrate far outside the X− ions in the [X−, e+] sta propose that a bubble is formed around the [X−, e+] state, similar to the Ps bubble found in nearly all liquids. F−ions did not react w Preliminary results showed that CN− ions react with eaq+ while OH−ions are non...... in the Cl− case) at higher concentrations. This saturation and the high-concentration effects-in the angular correlation results were interpreted as caused by rather complicated spur effects, wh It is proposed that spur electrons may pick off the positron from the [X−, e+ states with an efficiency which...

  9. Unusual solvation through both p-orbital lobes of a carbene carbon

    Energy Technology Data Exchange (ETDEWEB)

    Hadad, C. Z., E-mail: cacier.hadad@udea.edu.co [Grupo de Química-Física Teórica, Instituto de Química, Universidad de Antioquia, A. A. 1226 Medellín (Colombia); Jenkins, Samantha [College of Chemistry and Chemical Engineering, Hunan Normal University, Changsha, Hunan 410081 (China); Flórez, Elizabeth [Departamento de Ciencias Básicas, Universidad de Medellín, Carrera 87 N° 30-65, Medellín (Colombia)

    2015-03-07

    As a result of a configurational space search done to explain the experimental evidence of transient specific solvation of singlet fluorocarbene amide with tetrahydrofuran, we found that the most stable structures consist in a group in which each oxygen of two tetrahydrofuran molecules act as electron donor to its respective empty p-orbital lobe of the carbene carbon atom, located at each side of the carbene molecular plane. This kind of species, which to our knowledge has not been reported before, explains very well the particular experimental characteristics observed for the transient solvation of this system. We postulate that the simultaneous interaction to both p-orbital lobes seems to confer a special stability to the solvation complexes, because this situation moves away the systems from the proximity of the corresponding transition states for the ylide products. Additionally, we present an analysis of other solvation complexes and a study of the nature of the involved interactions.

  10. Transmission Electron Microscopy of a CMSX-4 Ni-Base Superalloy Produced by Selective Electron Beam Melting

    Directory of Open Access Journals (Sweden)

    Alireza B. Parsa

    2016-10-01

    Full Text Available In this work, the microstructures of superalloy specimens produced using selective electron beam melting additive manufacturing were characterized. The materials were produced using a CMSX-4 powder. Two selective electron beam melting processing strategies, which result in higher and lower effective cooling rates, are described. Orientation imaging microscopy, scanning transmission electron microscopy and conventional high resolution transmission electron microscopy are used to investigate the microstructures. Our results suggest that selective electron beam melting processing results in near equilibrium microstructures, as far as γ′ volume fractions, the formation of small amounts of TCP phases and the partitioning behavior of the alloy elements are concerned. As expected, higher cooling rates result in smaller dendrite spacings, which are two orders of magnitude smaller than observed during conventional single crystal casting. During processing, columnar grains grow in <100> directions, which are rotated with respect to each other. There are coarse γ/γ′ microstructures in high angle boundary regions. Dislocation networks form low angle boundaries. A striking feature of the as processed selective electron beam melting specimens is their high dislocation density. From a fundamental point of view, this opens new possibilities for the investigation of elementary dislocation processes which accompany solidification.

  11. On some methods to produce high-energy polarized electron beams by means of proton synchrotrons

    International Nuclear Information System (INIS)

    Bessonov, E.G.; Vazdik, Ya.A.

    1980-01-01

    Some methods of production of high-energy polarized electron beams by means of proton synchrotrons are considered. These methods are based on transfer by protons of a part of their energy to the polarized electrons of a thin target placed inside the working volume of the synchrotron. It is suggested to use as a polarized electron target a magnetized crystalline iron in which proton channeling is realized, polarized atomic beams and the polarized plasma. It is shown that by this method one can produce polarized electron beams with energy approximately 100 GeV, energy spread +- 5 % and intensity approximately 10 7 electron/c, polarization approximately 30% and with intensity approximately 10 4 -10 5 electron/c, polarization approximately 100% [ru

  12. Updated Abraham solvation parameters for polychlorinated biphenyls

    NARCIS (Netherlands)

    van Noort, P.C.M.; Haftka, J.J.H.; Parsons, J.R.

    2010-01-01

    This study shows that the recently published polychlorinated biphenyl (PCB) Abraham solvation parameters predict PCB air−n-hexadecane and n-octanol−water partition coefficients very poorly, especially for highly ortho-chlorinated congeners. Therefore, an updated set of PCB solvation parameters was

  13. Updated Abraham solvation parameters for polychlorinated biphenyls

    NARCIS (Netherlands)

    Noort, van P.C.M.; Haftka, J.J.H.; Parsons, J.R.

    2010-01-01

    This study shows that the recently published polychlorinated biphenyl (PCB) Abraham solvation parameters predict PCB air-n-hexadecane and n-octanol-water partition coefficients very poorly, especially for highly ortho-chlorinated congeners. Therefore, an updated set of PCB solvation parameters was

  14. Characterization of the fast electrons distribution produced in a high intensity laser target interaction

    Energy Technology Data Exchange (ETDEWEB)

    Westover, B. [Department of Mechanical and Aerospace Engineering, University of California San Diego, La Jolla, California 92093 (United States); Lawrence Livermore National Laboratory, Livermore, California 94550 (United States); Chen, C. D.; Patel, P. K.; McLean, H. [Lawrence Livermore National Laboratory, Livermore, California 94550 (United States); Beg, F. N., E-mail: fbeg@ucsd.edu [Department of Mechanical and Aerospace Engineering, University of California San Diego, La Jolla, California 92093 (United States)

    2014-03-15

    Experiments on the Titan laser (∼150 J, 0.7 ps, 2 × 10{sup 20} W cm{sup −2}) at the Lawrence Livermore National Laboratory were carried out in order to study the properties of fast electrons produced by high-intensity, short pulse laser interacting with matter under conditions relevant to Fast Ignition. Bremsstrahlung x-rays produced by these fast electrons were measured by a set of compact filter-stack based x-ray detectors placed at three angles with respect to the target. The measured bremsstrahlung signal allows a characterization of the fast electron beam spectrum, conversion efficiency of laser energy into fast electron kinetic energy and angular distribution. A Monte Carlo code Integrated Tiger Series was used to model the bremsstrahlung signal and infer a laser to fast electron conversion efficiency of 30%, an electron slope temperature of about 2.2 MeV, and a mean divergence angle of 39°. Simulations were also performed with the hybrid transport code ZUMA which includes fields in the target. In this case, a conversion efficiency of laser energy to fast electron energy of 34% and a slope temperature between 1.5 MeV and 4 MeV depending on the angle between the target normal direction and the measuring spectrometer are found. The observed temperature of the bremsstrahlung spectrum, and therefore the inferred electron spectrum are found to be angle dependent.

  15. Study of electrons distribution produced by laser-plasma interaction on x-ray generation

    International Nuclear Information System (INIS)

    Nikzad, L.; Sadighi-Bonabi, R.

    2010-01-01

    Complete text of publication follows. In the present work, X-ray beams are generated from interaction of relativistic electron beams produced by interaction of 500 mJ, 30 femtosecond Ti:sapphire laser pulses with thin solid targets such as lead, molybdenum and tungsten. After interaction of an intense pulsed laser with He gas-jet, a micron-scale laser produced plasma, creates and accelerates electron bunches, which propagate in the ion channel produced in the wake of the laser pulse. When an electron bunch is injected into the bubble in phase with its field, it will gain relativistic energies within very short distance. These accelerated electrons with Megaelectron-Volt energy and different distributions, can interact with targets to generate X-ray radiation with Kiloelectron-Volt energy, providing to be close enough to the gas-jet, where the relativistic accelerated electrons exist. Here, to determine the results, Monte Carlo simulation (MCNP-4C code) is employed to present Bremsstrahlung and characteristic X-ray production by quasi-Maxwellian and quasi-monoenergetic electron beams for three samples with different thicknesses. The outcome shows that for one specific electron spectrum and one definite target, the energy which the maximum characteristic x-ray flux takes place, varies with thickness. Also, for each material the energy which this maximum happens is constant for all thicknesses, for both produced electron spectra. For each sample, x-ray flux is calculated for different thicknesses and the thickness which the maximum characteristic x-ray flux occurs is obtained. Besides, it is concluded that by increasing the atomic number of the target, maximum X-ray flux moves towards higher energy. Also, comparison of the results for three targets and two electron distributions shows that by using quasi-monoenergetic electron spectra, more intense and narrower characteristic X-ray can be produced compared to the quasi-Maxwellian electron distribution, almost for all

  16. Precision gamma-ray polarimetry applied to studies of bremsstrahlung produced by polarized electrons

    Energy Technology Data Exchange (ETDEWEB)

    Kovtun, Oleksiy

    2015-12-16

    The thesis reports on the measurement of bremsstrahlung linear polarization produced in collisions of longitudinally and transversely polarized electrons with gold atoms. The experiment was performed at the Mainzer Microtron MAMI in the Institut fuer Kernphysik of Johannes Gutenberg-Universitaet Mainz, Germany. Spin-oriented electrons with 2.15 MeV kinetic energy collided with a thin golden target and produced bremsstrahlung. Linear polarization of the emitted photons was measured by means of Compton polarimetry applied to a segmented high-purity germanium detector. Experimental results reveal a strong correlation between the electron spin orientation and bremsstrahlung linear polarization. This indicates a dominant role of the electron spin in atomic-field bremsstrahlung and Coulomb scattering.

  17. Ionic Liquids: Radiation Chemistry, Solvation Dynamics and Reactivity Patterns

    International Nuclear Information System (INIS)

    Wishart, J.F.

    2008-01-01

    Ionic liquids (ILs) are a rapidly expanding family of condensed-phase media with important applications in energy production, nuclear fuel and waste processing, improving the efficiency and safety of industrial chemical processes, and pollution prevention. ILs are generally nonvolatile, noncombustible, highly conductive, recyclable and capable of dissolving a wide variety of materials. They are finding new uses in chemical synthesis, catalysis, separations chemistry, electrochemistry and other areas. Ionic liquids have dramatically different properties compared to conventional molecular solvents, and they provide a new and unusual environment to test our theoretical understanding of charge transfer and other reactions. We are interested in how IL properties influence physical and dynamical processes that determine the stability and lifetimes of reactive intermediates and thereby affect the courses of chemical reactions and product distributions. Successful use of ionic liquids in radiation-filled environments, where their safety advantages could be significant, requires an understanding of ionic liquid radiation chemistry. For example, characterizing the primary steps of IL radiolysis will reveal radiolytic degradation pathways and suggest ways to prevent them or mitigate their effects on the properties of the material. An understanding of ionic liquid radiation chemistry will also facilitate pulse radiolysis studies of general chemical reactivity in ILs, which will aid in the development of applications listed above. Very early in our radiolysis studies it became evident that slow solvation dynamics of the excess electron in ILs (which vary over a wide viscosity range) increases the importance of pre-solvated electron reactivity and consequently alters product distributions. Parallel studies of IL solvation phenomena using coumarin-153 dynamic Stokes shifts and polarization anisotropy decay rates are done to compare with electron solvation studies and to evaluate

  18. IONIC LIQUIDS: RADIATION CHEMISTRY, SOLVATION DYNAMICS AND REACTIVITY PATTERNS

    International Nuclear Information System (INIS)

    WISHART, J.F.

    2007-01-01

    energy production, nuclear fuel and waste processing, improving the efficiency and safety of industrial chemical processes, and pollution prevention. ILs are generally nonvolatile, noncombustible, highly conductive, recyclable and capable of dissolving a wide variety of materials. They are finding new uses in chemical synthesis, catalysis, separations chemistry, electrochemistry and other areas. Ionic liquids have dramatically different properties compared to conventional molecular solvents, and they provide a new and unusual environment to test our theoretical understanding of charge transfer and other reactions. We are interested in how IL properties influence physical and dynamical processes that determine the stability and lifetimes of reactive intermediates and thereby affect the courses of chemical reactions and product distributions. Successful use of ionic liquids in radiation-filled environments, where their safety advantages could be significant, requires an understanding of ionic liquid radiation chemistry. For example, characterizing the primary steps of IL radiolysis will reveal radiolytic degradation pathways and suggest ways to prevent them or mitigate their effects on the properties of the material. An understanding of ionic liquid radiation chemistry will also facilitate pulse radiolysis studies of general chemical reactivity in ILs, which will aid in the development of applications listed above. Very early in our radiolysis studies it became evident that slow solvation dynamics of the excess electron in ILs (which vary over a wide viscosity range) increases the importance of pre-solvated electron reactivity and consequently alters product distributions. Parallel studies of IL solvation phenomena using coumarin-153 dynamic Stokes shifts and polarization anisotropy decay rates are done to compare with electron solvation studies and to evaluate the influence of ILs on charge transport processes. Methods. Picosecond pulse radiolysis studies at BNL

  19. On the usage of electron beam as a tool to produce radioactive isotopes in photonuclear reactions

    International Nuclear Information System (INIS)

    Bunatyan, G.G.; Nikolenko, V.G.; Popov, A.B.

    2009-01-01

    We treat the Bremsstrahlung, induced by initial electron beam in converter, and the production of a desirable radioisotope due to the photonuclear reaction caused by this Bremsstrahlung. By way of illustration, the yield of a number of some, the most applicable in practice, radioisotopes is evaluated. The acquired findings persuade us that usage of modern electron accelerators offers a practicable way to produce the radioisotopes needful nowadays for various valuable applications in the nuclear medicine

  20. On the average luminosity of electron positron collider and positron-producing energy

    International Nuclear Information System (INIS)

    Xie Jialin

    1985-01-01

    In this paper, the average luminosity of linac injected electron positron collider is investigated from the positron-producing energy point of view. When the energy of the linac injector is fixed to be less than the operating energy of the storage ring, it has been found that there exists a positron-producing energy to give optimum average luminosity. Two cases have been studied, one for an ideal storage ring with no single-beam instability and the other for practical storage ring with fast head-tail instability. The result indicates that there is a positron-producing energy corresponding to the minimum injection time, but this does not correspond to the optimum average luminosity for the practical storage rings. For Beijing Electron Positron Collider (BEPC), the positron-producing energy corresponding to the optimum average luminosity is about one tenth of the total injector energy

  1. Theory of electron degradation and yields of initial molecular species produced by ionizing radiation

    International Nuclear Information System (INIS)

    Inokuti, M.; Dillon, M.A.; Kimura, M.

    1987-01-01

    Ionizing radiations generate in matter a large number of energetic electrons, which in turn collide with molecules in matter, produce ions and excited states, and thereby degrade in energy. The description of the consequences of many collision processes to the electrons and to matter is the goal of the electron degradation theory. They summarize the current understanding of this topic, which is important as a basis of radiation chemistry and biology. In addition, they present an initial report of their new work, namely, a generalization of the Spencer-Fano theory to time-dependent cases

  2. Calculation of electron contamination doses produced using blocking trays for 6 MV X-rays

    Energy Technology Data Exchange (ETDEWEB)

    Butson, M.J. E-mail: mbutson@guessmail.com; Cheung Tsang; Yu, P.K.N

    2002-04-01

    Calculation of electron contamination doses whilst using blocking trays in radiotherapy is achieved by comparison of measured absorbed dose within the first few centimeters of a water phantom. Electron contamination of up to 28% of maximum dose is produced at the central axis of the beam whilst using a 6 mm Perspex blocking tray for a 30 cmx30 cm field. The electron contamination is spread over the entire field reducing slightly towards the edge of the beam. Electron contamination from block trays is also present outside the primary collimated X-ray beam with more than 20% of the maximum dose deposited at the surface, 5 cm outside the primary collimated beam at a field size of 40 cmx40 cm. The electron contamination spectrum has been calculated from measured results.

  3. Relativistic electron drift in overdense plasma produced by a superintense femtosecond laser pulse

    International Nuclear Information System (INIS)

    Rastunkov, V.S.; Krainov, V.P.

    2004-01-01

    The general peculiarities of electron motion in the skin layer at the irradiation of overdense plasma by a superintense linearly polarized laser pulse of femtosecond duration are considered. The quiver electron energy is assumed to be a relativistic quantity. Relativistic electron drift along the propagation of laser radiation produced by a magnetic part of a laser field remains after the end of the laser pulse, unlike the relativistic drift of a free electron in underdense plasma. As a result, the penetration depth is much larger than the classical skin depth. The conclusion has been made that the drift velocity is a nonrelativistic quantity even at the peak laser intensity of 10 21 W/cm 2 . The time at which an electron penetrates into field-free matter from the skin layer is much less than the pulse duration

  4. Ion Flux Measurements in Electron Beam Produced Plasmas in Atomic and Molecular Gases

    Science.gov (United States)

    Walton, S. G.; Leonhardt, D.; Blackwell, D. D.; Murphy, D. P.; Fernsler, R. F.; Meger, R. A.

    2001-10-01

    In this presentation, mass- and time-resolved measurements of ion fluxes sampled from pulsed, electron beam-generated plasmas will be discussed. Previous works have shown that energetic electron beams are efficient at producing high-density plasmas (10^10-10^12 cm-3) with low electron temperatures (Te < 1.0 eV) over the volume of the beam. Outside the beam, the plasma density and electron temperature vary due, in part, to ion-neutral and electron-ion interactions. In molecular gases, electron-ion recombination plays a significant role while in atomic gases, ion-neutral interactions are important. These interactions also determine the temporal variations in the electron temperature and plasma density when the electron beam is pulsed. Temporally resolved ion flux and energy distributions at a grounded electrode surface located adjacent to pulsed plasmas in pure Ar, N_2, O_2, and their mixtures are discussed. Measurements are presented as a function of operating pressure, mixture ratio, and electron beam-electrode separation. The differences in the results for atomic and molecular gases will also be discussed and related to their respective gas-phase kinetics.

  5. Solvates of silico-12-molybdic acid with alcohols

    International Nuclear Information System (INIS)

    Punchuk, I.N.; Chuvaev, V.F.

    1984-01-01

    With the aim of investigating interaction processes of solid heteropolyacids and organic compounds, solvates are prepared. Solvates are products of adding gaseous methanol, ethanol and isopropanol to silico-12-molybdic acid. The compounds are studied by IR and PMR spectroscopy methods. Possible models for solvate structure are considered, as well as their connection with solvate properties and thermal decomposition

  6. Few femtosecond, few kilo-ampere electron bunch produced by a laser-plasma accelerator

    International Nuclear Information System (INIS)

    Lundh, O.; Lim, J.; Rechatin, C.; Ammoura, L.; Goddet, J.P.; Malka, V.; Faure, J.; Ben-Ismail, A.; Davoine, X.; Lefebvre, E.; Gallot, G.

    2011-01-01

    Particle accelerators driven by the interaction of ultra-intense and ultrashort laser pulses with a plasma can generate accelerating electric fields of several hundred giga-volts per meter and deliver high-quality electron beams with low energy spread, low emittance and up to 1 GeV peak energy. Moreover, it is expected they may soon be able to produce bursts of electrons shorter than those produced by conventional particle accelerators, down to femtosecond durations and less. Here we present wide-band spectral measurements of coherent transition radiation which we use for temporal characterization. Our analysis shows that the electron beam, produced using controlled optical injection, contains a temporal feature that can be identified as a 15 pC, 1.4-1.8 fs electron bunch (root mean square) leading to a peak current of 3-4 kA depending on the bunch shape. We anticipate that these results will have a strong impact on emerging applications such as short-pulse and short-wavelength radiation sources, and will benefit the realization of laboratory-scale free-electron lasers. (authors)

  7. Time-resolved energy spectrum of a pseudospark-produced high-brightness electron beam

    International Nuclear Information System (INIS)

    Myers, T.J.; Ding, B.N.; Rhee, M.J.

    1992-01-01

    The pseudospark, a fast low-pressure gas discharge between a hollow cathode and a planar anode, is found to be an interesting high-brightness electron beam source. Typically, all electron beam produced in the pseudospark has the peak current of ∼1 kA, pulse duration of ∼50 ns, and effective emittance of ∼100 mm-mrad. The energy information of this electron beam, however, is least understood due to the difficulty of measuring a high-current-density beam that is partially space-charge neutralized by the background ions produced in the gas. In this paper, an experimental study of the time-resolved energy spectrum is presented. The pseudospark produced electron beam is injected into a vacuum through a small pinhole so that the electrons without background ions follow single particle motion; the beam is sent through a negative biased electrode and the only portion of beam whose energy is greater than the bias voltage can pass through the electrode and the current is measured by a Faraday cup. The Faraday cup signals with various bias voltage are recorded in a digital oscilloscope. The recorded waveforms are then numerically analyzed to construct a time-resolved energy spectrum. Preliminary results are presented

  8. Investigation of plasma stream collision produced by thin films irradiated by powerful pulsed electron beam

    International Nuclear Information System (INIS)

    Efremov, V P; Demidov, B A; Ivkin, M V; Mescheryakov, A N; Petrov, V A; Potapenko, A I

    2006-01-01

    Collision of fast plasma streams in vacuum is investigated. Plasma streams were produced by irradiation of thin foils with a powerful pulsed electron beam. Interaction of the plasma flows was studied by using frame and streak cameras. One-dimensional numerical simulation was carried out. Application of this method for porous ICF targets and high-energy physics is discussed

  9. Shielding required for radiation produced by 15 GeV stored electrons

    International Nuclear Information System (INIS)

    Jenkins, T.M.; McCaslin, J.B.; Thomas, R.H.

    1974-01-01

    The first phase of PEP will consist of a 15 GeV electron and positron storage ring. This note examines the shielding required by such a facility. Shielding of neutrons and muons produced by 200 GeV protons in the second phase of PEP has been discussed in previous notes. 9 refs., 9 figs., 5 tabs

  10. Radiation-produced electron migration along 5-bromouracil-substituted DNA in cells and in solutions

    International Nuclear Information System (INIS)

    Beach, C.M.

    1981-01-01

    Results of work by other investigators support the theory of charge migration in DNA. Charge transfer between nucleotides and electron and energy migration in solid state DNA have been detected, but no previous experiments have demonstrated charge migration in aqueous solutions of DNA or in DNA inside an E. coli cell. Such experiments were performed by substituting different amounts of 5-bromouracil (BU) for thymine in E. coli DNA and assaying for the amount of bromide given off from the reaction of bromouracil with hydrated electrons produced by ionizing radiation to form uracil-5-yl radicals and free bromide. By varying the amount of BU incorporated in the DNA, the average distance between the BU bases was varied, and because the number of BU/electron reactions was monitored by the amount of bromide released, the maximum average electron migration distance along the BU-DNA was estimated. Charge migration was demonstrated, and the maximum average electron migration distance in aqueous solutions of BU-DNA was measured to be 8 to 10 base distances (assuming only intrastrand migration). Only 11 to 16% of the electrons produced attacked BU-DNA in aqueous solution, and only 1% resulted in bromide release from BU-DNA inside E. coli. Charge migration was demonstrated in BU-DNA inside E. coli, and the maximum average migration distance was measured to be 5 to 6 base distances

  11. Radiation-produced electron migration along 5-bromouracil-substituted DNA in cells and in solutions

    International Nuclear Information System (INIS)

    Beach, C.M.

    1981-01-01

    Results of work by other investigators support the theory of charge migration in DNA. Charge transfer between nucleotides and electron and energy migration in solid state DNA have been detected, but no previous experiments have demonstrated charge migration in aqueous solutions of DNA or in DNA inside an E. coli cell. Such experiments were performed by substituting different amounts of 5-bromouracil (BU) for thymine in E. coli DNA and assaying for the amount of bromide given off from the reaction of bromouracil with hydrated electrons produced by ionizing radiation to form uracil-5-yl radicals and free bromide. By varying the amount of BU incorporated in the DNA, the average distance between the BU bases was varied, and because the number of BU/electron reactions was monitored by the amount of bromide released, the maximum average electron migration distance along the BU-DNA was estimated. Hydrated electrons, e/sub aq/, were shown to react with BU in BU-DNA with the resultant release of bromide with G(-BR - ) = 0.519 +- 0.062. OH radicals were half as reactive as e/sub aq/ toward producing bromide from BU-DNA. O 2 , which has been shown to transfer charge to BU in aqueous solution, did not transfer charge to BU-DNA. The CO 2 radical was shown to cause the release of bromide from BU-DNA at least as effectively as e/sub aq/. Charge migration was demonstrated, and the maximum average electron migration distance in aqueous solutions of BU-DNA was measured to be 8 to 10 base distances (assuming only intrastrand migration). Only 11% to 16% of the electrons produced attacked BU-DNA in aqueous solution, and only 1% resulted in bromide release from BU-DNA inside E. coli. Charge migration was demonstrated in BU-DNA inside E. coli., and the maximum average migration distance was measured to be 5 to 6 base distances

  12. Pencil-like mm-size electron beams produced with linear inductive voltage adders (LIVA)

    International Nuclear Information System (INIS)

    Mazarakis, M.G.; Poukey, J.W.; Rovang, D.C.

    1996-01-01

    This paper presents design, analysis, and first results of the high brightness electron beam experiments currently under investigation at Sandia. Anticipated beam parameters are: energy 12 MeV, current 35-40 kA, rms radius 0.5 mm, pulse duration 40 ns FWHM. The accelerator is SABRE, a pulsed LIVA modified to higher impedance, and the electron source is a magnetically immersed foilless electron diode. 20 to 30 Tesla solenoidal magnets are required to insulate the diode and contain the beam to its extremely small sized (1 mm) envelope. These experiments are designed to push the technology to produce the highest possible electron current in a submillimeter radius beam. Design, numercial simulations, and first experimental results are presented

  13. Pencil-like mm-size electron beams produced with Linear Inductive Voltage Adders (LIVA)

    International Nuclear Information System (INIS)

    Mazarakis, M.G.; Poukey, J.W.; Rovang, D C.; Maenchen, J.E.; Cordova, S.R.; Menge, P.R.; Pepping, R.; Bennett, L.; Mikkelson, K.; Smith, D.L.; Halbleib, J.; Stygar, W.A.; Welch, D.R.

    1996-01-01

    We present the design, analysis, and first results of the high brightness electron beam experiments currently under investigation at Sandia National Laboratories. The anticipated beam parameters are the following: energy 12 MeV, current 35-40 kA, rms radius 0.5 mm, and pulse duration 40 ns FWHM. The accelerator is SABRE, a pulsed LIVA modified to higher impedance, and the electron source is a magnetically immersed foilless electron diode. Twenty to thirty Tesla solenoidal magnets are required to insulate the diode and contain the beam to its extremely small sized (1 mm) envelope. These experiments are designed to push the technology to produce the highest possible electron current in a submillimeter radius beam. Design, numerical simulations, and first experimental results are presented. (author)

  14. Electron-Beam Produced Air Plasma: Optical Measurement of Beam Current

    Science.gov (United States)

    Vidmar, Robert; Stalder, Kenneth; Seeley, Megan

    2006-10-01

    Experiments to quantify the electron beam current and distribution of beam current in air plasma are discussed. The air plasma is produced by a 100-keV 10-mA electron beam source that traverses a transmission window into a chamber with air as a target gas. Air pressure is between 1 mTorr and 760 Torr. Strong optical emissions due to electron impact ionization are observed for the N2 2^nd positive line at 337.1 nm and the N2^+ 1^st negative line at 391.4 nm. Calibration of optical emissions using signals from the isolated transmission window and a Faraday plate are discussed. The calibrated optical system is then used to quantify the electron distribution in the air plasma.

  15. Observations of visual sensations produced by Cerenkov radiation from high-energy electrons

    International Nuclear Information System (INIS)

    Steidley, K.D.; Eastman, R.M.; Stabile, R.J.

    1989-01-01

    Ten cancer patients whose eyes were therapeutically irradiated with 6-18 MeV electrons reported visual light sensations. Nine reported seeing blue light and one reported seeing white light. Controls reported seeing no light. Additionally, tests with patients ruled out the x-ray contamination of the electron beam as being important. The photon yield due to Cerenkov radiation produced by radium and its daughters for both electrons and gamma rays was calculated; it was found to account for a turn-of-the-century human observation of the radium phosphene. We conclude that the dominant mechanism of this phosphene is Cerenkov radiation, primarily from betas. From our own patient data, based on the color seen and the Cerenkov production rates, we conclude that the dominant mechanism is Cerenkov radiation and that high-energy electrons are an example of particle induced visual sensations

  16. Modification of a scanning electron microscope to produce Smith-Purcell radiation

    International Nuclear Information System (INIS)

    Kapp, Oscar H.; Sun, Yin-e; Kim, Kwang-Je; Crewe, Albert V.

    2004-01-01

    We have modified a scanning electron microscope (SEM) in an attempt to produce a miniature free electron laser that can produce radiation in the far infrared region, which is difficult to obtain otherwise. This device is similar to the instrument studied by the Dartmouth group and functions on the basic principles first described by Smith and Purcell. The electron beam of the SEM is passed over a metal grating and should be capable of producing photons either in the spontaneous emission regime or in the superradiance regime if the electron beam is sufficiently bright. The instrument is capable of being continuously tuned by virtue of the period of the metal grating and the choice of accelerating voltage. The emitted Smith-Purcell photons exit the instrument via a polyethylene window and are detected by an infrared bolometer. Although we have obtained power levels exceeding nanowatts in the spontaneous emission regime, we have thus far not been able to detect a clear example of superradiance

  17. Physiological Evidence for Isopotential Tunneling in the Electron Transport Chain of Methane-Producing Archaea.

    Science.gov (United States)

    Duszenko, Nikolas; Buan, Nicole R

    2017-09-15

    Many, but not all, organisms use quinones to conserve energy in their electron transport chains. Fermentative bacteria and methane-producing archaea (methanogens) do not produce quinones but have devised other ways to generate ATP. Methanophenazine (MPh) is a unique membrane electron carrier found in Methanosarcina species that plays the same role as quinones in the electron transport chain. To extend the analogy between quinones and MPh, we compared the MPh pool sizes between two well-studied Methanosarcina species, Methanosarcina acetivorans C2A and Methanosarcina barkeri Fusaro, to the quinone pool size in the bacterium Escherichia coli We found the quantity of MPh per cell increases as cultures transition from exponential growth to stationary phase, and absolute quantities of MPh were 3-fold higher in M. acetivorans than in M. barkeri The concentration of MPh suggests the cell membrane of M. acetivorans , but not of M. barkeri , is electrically quantized as if it were a single conductive metal sheet and near optimal for rate of electron transport. Similarly, stationary (but not exponentially growing) E. coli cells also have electrically quantized membranes on the basis of quinone content. Consistent with our hypothesis, we demonstrated that the exogenous addition of phenazine increases the growth rate of M. barkeri three times that of M. acetivorans Our work suggests electron flux through MPh is naturally higher in M. acetivorans than in M. barkeri and that hydrogen cycling is less efficient at conserving energy than scalar proton translocation using MPh. IMPORTANCE Can we grow more from less? The ability to optimize and manipulate metabolic efficiency in cells is the difference between commercially viable and nonviable renewable technologies. Much can be learned from methane-producing archaea (methanogens) which evolved a successful metabolic lifestyle under extreme thermodynamic constraints. Methanogens use highly efficient electron transport systems and

  18. Semi-empirical model for the generation of dose distributions produced by a scanning electron beam

    International Nuclear Information System (INIS)

    Nath, R.; Gignac, C.E.; Agostinelli, A.G.; Rothberg, S.; Schulz, R.J.

    1980-01-01

    There are linear accelerators (Sagittaire and Saturne accelerators produced by Compagnie Generale de Radiologie (CGR/MeV) Corporation) which produce broad, flat electron fields by magnetically scanning the relatively narrow electron beam as it emerges from the accelerator vacuum system. A semi-empirical model, which mimics the scanning action of this type of accelerator, was developed for the generation of dose distributions in homogeneous media. The model employs the dose distributions of the scanning electron beams. These were measured with photographic film in a polystyrene phantom by turning off the magnetic scanning system. The mean deviation calculated from measured dose distributions is about 0.2%; a few points have deviations as large as 2 to 4% inside of the 50% isodose curve, but less than 8% outside of the 50% isodose curve. The model has been used to generate the electron beam library required by a modified version of a commercially-available computerized treatment-planning system. (The RAD-8 treatment planning system was purchased from the Digital Equipment Corporation. It is currently available from Electronic Music Industries

  19. 1 SUPPLEMENTARY INFORMATION Nonpolar Solvation Dynamics ...

    Indian Academy of Sciences (India)

    IITP

    . S. NP. ( t. ) ( )t. SNeqm. NP. (a). (b). Figure S2. (a) Nonequilibrium solvation response functions calculated after averaging over different number of nonequilibrium trajectories. The response function converges after averaging over more than ...

  20. Spectral measurements of few-electron uranium ions produced and trapped in a high-energy electron beam ion trap

    International Nuclear Information System (INIS)

    Beiersdorfer, P.

    1994-01-01

    Measurements of 2s l/2 -2p 3/2 electric dipole and 2p 1/2 -2p 3/2 magnetic dipole and electric quadrupole transitions in U 82+ through U 89+ have been made with a high-resolution crystal spectrometer that recorded the line radiation from stationary ions produced and trapped in a high-energy electron beam ion trap. From the measurements we infer -39.21 ± 0.23 eV for the QED contribution to the 2s 1/2 -2p 3/2 transition energy of lithiumlike U 89+ . A comparison between our measurements and various computations illustrates the need for continued improvements in theoretical approaches for calculating the atomic structure of ions with two or more electrons in the L shell

  1. Post acceleration of a pseudospark-produced electron beam by an induction linac

    International Nuclear Information System (INIS)

    Ding, B.N.; Myers, T.J.; Rhee, M.J.

    1992-01-01

    Recently, a high-brightness electron beam produced by a simple pseudospark device has been reported. Typically, the electron beam has a peak current of up to 1 kA, FWHM pulse duration of 30 ns, and an effective emittance of 4[ 2 > r2 > - 2] 1/2 = 100 mm-mrad. The normalized brightness of the beam is estimated to be on the order of 10 11 A/(m 2 -rad 2 ). This high-brightness beam may be immediately useful for high current accelerators and free-electron lasers if the beam energy can be boosted up. In this paper, the authors present preliminary results of the post acceleration of the electron beam by using an induction linac. The pseudospark device is modified by adding a trigger electrode in the hollow cavity of the cathode so that the generation of the electron beam is synchronized with the induction linac. A simple induction linac system of 25 kV, 1 kA, 50 ns pulse is being constructed. The electron beam, which is born in a low pressure gas, will be accelerated in the same background gas. This gas provides a sufficient ion channel for necessary focusing of this high-current density beam. Preliminary results on the beam current, energy spectrum, and emittance measurements of the post-accelerated beam will be presented

  2. Photo-triggering and secondary electron produced ionization in electric discharge ArF* excimer lasers

    Science.gov (United States)

    Xiong, Zhongmin; Kushner, Mark J.

    2011-10-01

    Electric discharge excimer lasers are sustained in multi-atmosphere attaching gas mixtures that are typically preionized to enable a reproducible, uniform glow, which maximizes optical quality and gain. This preionization is often accomplished using UV light produced by a corona discharge within the plasma cavity. To quantify the relationship between corona discharge properties and those of the laser discharge, the triggering of electron avalanche by preionizing UV light in an electric discharge-pumped ArF* excimer laser was numerically investigated using a two-dimensional model. The preionizing UV fluxes were generated by a corona-bar discharge driven by the same voltage pulse as the main discharge sustained in a multi-atmospheric Ne/Ar/Xe/F2 gas mixture. The resulting peak photo-electron density in the inter-electrode spacing is around 108 cm-3, and its distribution is biased toward the UV source. The preionization density increases with increasing dielectric constant and capacitance of the corona bar. The symmetry and uniformity of the discharge are, however, improved significantly once the main avalanche develops. In addition to bulk electron impact ionization, the ionization generated by sheath accelerated secondary electrons was found to be important in sustaining the discharge current at experimentally observed values. At peak current, the magnitude of the ionization by sheath accelerated electrons is comparable to that from bulk electron impact in the vicinity of the cathode.

  3. Simultaneous streak and frame interferometry for electron density measurements of laser produced plasmas

    Energy Technology Data Exchange (ETDEWEB)

    Quevedo, H. J., E-mail: hjquevedo@utexas.edu; McCormick, M.; Wisher, M.; Bengtson, Roger D.; Ditmire, T. [Center for High Energy Density Science, Department of Physics, University of Texas at Austin, Austin, Texas 78712 (United States)

    2016-01-15

    A system of two collinear probe beams with different wavelengths and pulse durations was used to capture simultaneously snapshot interferograms and streaked interferograms of laser produced plasmas. The snapshots measured the two dimensional, path-integrated, electron density on a charge-coupled device while the radial temporal evolution of a one dimensional plasma slice was recorded by a streak camera. This dual-probe combination allowed us to select plasmas that were uniform and axisymmetric along the laser direction suitable for retrieving the continuous evolution of the radial electron density of homogeneous plasmas. Demonstration of this double probe system was done by measuring rapidly evolving plasmas on time scales less than 1 ns produced by the interaction of femtosecond, high intensity, laser pulses with argon gas clusters. Experiments aimed at studying homogeneous plasmas from high intensity laser-gas or laser-cluster interaction could benefit from the use of this probing scheme.

  4. Crossdressing to Backbeats: The Status of the Electroclash Producer and the Politics of Electronic Music

    Directory of Open Access Journals (Sweden)

    David Madden

    2012-11-01

    Full Text Available Addressing the international emergence of electroclash at the turn of the millenium, this article investigates the distinct character of the genre and its related production practices, both in and out of the studio. Electroclash combines the extended pulsing sections of techno, house and other dance musics with the trashier energy of rock and new wave. The genre signals an attempt to reinvigorate dance music with a sense of sexuality, personality and irony. Electroclash also emphasizes, rather than hides, the European, trashy elements of electronic dance music. The coming together of rock and electro is examined vis-à-vis the ongoing changing sociality of music production/distribution and the changing role of the producer. Numerous women, whether as solo producers, or in the context of collaborative groups, significantly contributed to shaping the aesthetics and production practices of electroclash, an anomaly in the history of popular music and electronic music, where the role of the producer has typically been associated with men. These changes are discussed in relation to the way electroclash producers Peaches, Le Tigre, Chicks on Speed, and Miss Kittin and the Hacker often used a hybrid approach to production that involves the integration of new(er technologies, such as laptops containing various audio production softwares with older, inexpensive keyboards, microphones, samplers and drum machines to achieve the ironic backbeat laden hybrid electro-rock sound.   

  5. Intravenous coronary angiography utilizing K-emission and bremsstrahlung X-rays produced by electron bombardment

    International Nuclear Information System (INIS)

    1992-01-01

    The screening of the general population for coronary artery disease would be practical if a method existed for visualizing the extent of occlusion after an intravenous injection of contrast agent. Measurements performed with synchrotron radiation at SSRL and NSLS have shown that such an intravenous angiography procedure would be possible with an intense source of monochromatic X-rays. Because of the high cost of an electron synchrotron, theoretical analysis and experiments using inanimate phantoms has been undertaken to demonstrate the feasibility of using the spectrum produced by two appropriately chosen anode materials when bombarded with electrons in the 100--500 keV energy range for angiography. By using the X-rays emitted at 120 degree to the incident electron direction, about 20--30% of the X-ray intensity would be due to K-emission lines. Calculations using the TIGERP Monte Carlo Code, have shown that high quality angiograms of human coronary arteries should be possible with a contrast agent containing ytterbium, if an electron beam pulses of 16 kJ were used for each anode target. The experimental program supported in part by the DOE has consisted of these theoretical calculations and experiments at the Dynamitron Electron Accelerator Facility at BNL

  6. Understanding Lithium Solvation and Diffusion through Topological Analysis of First-Principles Molecular Dynamics

    Energy Technology Data Exchange (ETDEWEB)

    Bhatia, Harsh [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Gyulassy, Attila [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Ong, Mitchell [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Lordi, Vincenzo [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Draeger, Erik [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Pask, John [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Pascucci, Valerio [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Bremer, Peer -Timo [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)

    2016-09-27

    The performance of lithium-ion batteries is strongly influenced by the ionic conductivity of the electrolyte, which depends on the speed at which Li ions migrate across the cell and relates to their solvation structure. The choice of solvent can greatly impact, both, the solvation and diffusivity of Li ions. In this work, we present our application of the topological techniques to extract and predict such behavior in the data generated by the first-principles molecular dynamics simulation of Li ions in an important organic solvent -ethylene carbonate. More specifically, we use the scalar topology of the electron charge density field to analyze the evolution of the solvation structures. This allows us to derive a parameter-free bond definition for lithium-oxygen bonds, to provide a quantitative measure for bond strength, and to understand the regions of influence of each atom in the simulation. This has provided new insights into how and under what conditions certain bonds may form and break. As a result, we can identify and, more importantly, predict, unstable configurations in solvation structures. This can be very useful in understanding when small changes to the atoms' movements can cause significantly different bond structures to evolve. Ultimately, this promises to allow scientists to explore lithium ion solvation and diffusion more systematically, with the aim of new insights and potentially accelerating the calculations themselves.

  7. Dose properties of x-ray beams produced by laser-wakefield-accelerated electrons

    International Nuclear Information System (INIS)

    Kainz, K K; Hogstrom, K R; Antolak, J A; Almond, P R; Bloch, C D

    2005-01-01

    Given that laser wakefield acceleration (LWFA) has been demonstrated experimentally to accelerate electron beams to energies beyond 25 MeV, it is reasonable to assess the ability of existing LWFA technology to compete with conventional radiofrequency linear accelerators in producing electron and x-ray beams for external-beam radiotherapy. We present calculations of the dose distributions (off-axis dose profiles and central-axis depth dose) and dose rates of x-ray beams that can be produced from electron beams that are generated using state-of-the-art LWFA. Subsets of an LWFA electron energy distribution were propagated through the treatment head elements (presuming an existing design for an x-ray production target and flattening filter) implemented within the EGSnrc Monte Carlo code. Three x-ray energy configurations (6 MV, 10 MV and 18 MV) were studied, and the energy width ΔE of the electron-beam subsets varied from 0.5 MeV to 12.5 MeV. As ΔE increased from 0.5 MeV to 4.5 MeV, we found that the off-axis and central-axis dose profiles for x-rays were minimally affected (to within about 3%), a result slightly different from prior calculations of electron beams broadened by scattering foils. For ΔE of the order of 12 MeV, the effect on the off-axis profile was of the order of 10%, but the central-axis depth dose was affected by less than 2% for depths in excess of about 5 cm beyond d max . Although increasing ΔE beyond 6.5 MeV increased the dose rate at d max by more than 10 times, the absolute dose rates were about 3 orders of magnitude below those observed for LWFA-based electron beams at comparable energies. For a practical LWFA-based x-ray device, the beam current must be increased by about 4-5 orders of magnitude. (note)

  8. Electron spin-lattice relaxation mechanisms of radiation produced trapped electrons and hydrogen atoms in aqueous and organic glassy matrices. Modulation of electron nuclear dipolar interaction by tunnelling modes in a glassy matrix. [. gamma. rays

    Energy Technology Data Exchange (ETDEWEB)

    Bowman, M K; Kevan, L [Wayne State Univ., Detroit, Mich. (USA). Dept. of Chemistry

    1977-01-01

    The spin lattice relaxation of trapped electrons in aqueous and organic glasses and trapped hydrogen atoms in phosphoric acid glass has been directly studied as a function of temperature by the saturation recovery method. Below 50 to 100 K, the major spin lattice relaxation mechanism involves modulation of the electron nuclear dipolar (END) interaction with nuclei in the radical's environment by tunnelling of those nuclei between two or more positions. This relaxation mechanism occurs with high efficiency and has a characteristic linear temperature dependence. The tunnelling nuclei around trapped electrons do not seem to involve the nearest neighbor nuclei which are oriented by the electron in the process of solvation. Instead the tunnelling nuclei typically appear to be next nearest neighbors to the trapped electron. The identities of the tunnelling nuclei have been deduced by isotopic substitution and are attributed to: Na in 10 mol dm/sup -3/ NaOH aqueous glass, ethyl protons in ethanol glass, methyl protons in methanol glass and methyl protons in MTHF glass. For trapped hydrogen atoms in phosphoric acid, the phosphorus nuclei appear to be the effective tunnelling nuclei. Below approximately 10 K the spin lattice relaxation is dominated by a temperature independent cross relaxation term for H atoms in phosphoric acid glass and for electrons in 10 mol dm/sup -3/ NaOH aqueous glass, but not for electrons in organic glasses. This is compared with recent electron-electron double resonance studies of cross relaxation in these glasses. The spin lattice relaxation of O/sup -/ formed in 10 mol dm/sup -3/ NaOH aqueous glass was also studied and found to be mainly dominated by a Raman process with an effective Debye temperature of about 100 K.

  9. Solvation of the fluorine containing anions and their lithium salts in propylene carbonate and dimethoxyethane.

    Science.gov (United States)

    Chaban, Vitaly

    2015-07-01

    Electrolyte solutions based on the propylene carbonate (PC)-dimethoxyethane (DME) mixtures are of significant importance and urgency due to emergence of lithium-ion batteries. Solvation and coordination of the lithium cation in these systems have been recently attended in detail. However, analogous information concerning anions (tetrafluoroborate, hexafluorophosphate) is still missed. This work reports PM7-MD simulations (electronic-structure level of description) to include finite-temperature effects on the anion solvation regularities in the PC-DME mixture. The reported result evidences that the anions appear weakly solvated. This observation is linked to the absence of suitable coordination sites in the solvent molecules. In the concentrated electrolyte solutions, both BF4(-) and PF6(-) prefer to exist as neutral ion pairs (LiBF4, LiPF6).

  10. Corrosion Thermodynamics of Magnesium and Alloys from First Principles as a Function of Solvation

    Science.gov (United States)

    Limmer, Krista; Williams, Kristen; Andzelm, Jan

    Thermodynamics of corrosion processes occurring on magnesium surfaces, such as hydrogen evolution and water dissociation, have been examined with density functional theory (DFT) to evaluate the effect of impurities and dilute alloying additions. The modeling of corrosion thermodynamics requires examination of species in a variety of chemical and electronic states in order to accurately represent the complex electrochemical corrosion process. In this study, DFT calculations for magnesium corrosion thermodynamics were performed with two DFT codes (VASP and DMol3), with multiple exchange-correlation functionals for chemical accuracy, as well as with various levels of implicit and explicit solvation for surfaces and solvated ions. The accuracy of the first principles calculations has been validated against Pourbaix diagrams constructed from solid, gas and solvated charged ion calculations. For aqueous corrosion, it is shown that a well parameterized implicit solvent is capable of accurately representing all but the first coordinating layer of explicit water for charged ions.

  11. Defect structures in YBa2Cu3O/sub 7-x/ produced by electron irradiation

    International Nuclear Information System (INIS)

    Kirk, M.A.; Baker, M.C.; Liu, J.Z.; Lam, D.J.; Weber, H.W.

    1987-12-01

    Defect structures in YBa 2 Cu 3 O/sub 7-x/ produced by electron irradiation at 300 0 K were investigated by transmission electron microscopy. Threshold energies for the production of visible defects were determined to be 152 keV and 131 keV (+- 7 keV) in directions near the a and b (b > a) axes (both perpendicular to c, the long axis in the orthorhombic structure), respectively. During above threshold irradiations in an electron flux of 3 x 10 18 cm -2 s -1 , extended defects were observed to form and grow to sizes of 10 to 50 nm over 1000 s in material thicknesses 20 to 200 nm. Such low electron threshold energies suggest oxygen atom displacements with recoil energies near 20 eV. The observation of movement of twin boundaries during irradiation just above threshold suggests movement of the basal plane oxygen atoms by direct displacement or defect migration processes. Crystals irradiated above threshold were observed after about 24 hours to have transformed to a structure heavily faulted on planes perpendicular to the c axis. 3 refs., 3 figs

  12. Measurement of electron beam polarization produced by photoemission from bulk GaAs using twisted light

    Science.gov (United States)

    Clayburn, Nathan; Dreiling, Joan; McCarter, James; Ryan, Dominic; Poelker, Matt; Gay, Timothy

    2012-06-01

    GaAs photocathodes produce spin polarized electron beams when illuminated with circularly polarized light with photon energy approximately equal to the bandgap energy [1, 2]. A typical polarization value obtained with bulk GaAs and conventional circularly polarized light is 35%. This study investigated the spin polarization of electron beams emitted from GaAs illuminated with ``twisted light,'' an expression that describes a beam of light having orbital angular momentum (OAM). In the experiment, 790nm laser light was focused to a near diffraction-limited spot size on the surface of the GaAs photocathode to determine if OAM might couple to valence band electron spin mediated by the GaAs lattice. Our polarization measurements using a compact retarding-field micro-Mott polarimeter [3] have established an upper bound on the polarization of the emitted electron beam of 2.5%. [4pt] [1] D.T. Pierce, F. Meier, P. Zurcher, Appl. Phys. Lett. 26 670 (1975).[0pt] [2] C.K. Sinclair, et al., PRSTAB 10 023501 (2007).[0pt] [3] J.L. McCarter, M.L. Stutzman, K.W. Trantham, T.G. Anderson, A.M. Cook, and T.J. Gay Nucl. Instrum. and Meth. A (2010).

  13. Using electronic clinical practice audits as needs assessment to produce effective continuing medical education programming.

    Science.gov (United States)

    Klein, Doug; Staples, John; Pittman, Carmen; Stepanko, Cheryl

    2012-01-01

    The traditional needs assessment used in developing continuing medical education programs typically relies on surveying physicians and tends to only capture perceived learning needs. Instead, using tools available in electronic medical record systems to perform a clinical audit on a physician's practice highlights physician-specific practice patterns. The purpose of this study was to test the feasibility of implementing an electronic clinical audit needs assessment process for family physicians in Canada. A clinical audit of 10 preventative care interventions and 10 chronic disease interventions was performed on family physician practices in Alberta, Canada. The physicians used the results from the audit to produce personalized learning needs, which were then translated into educational programming. A total of 26 family practices and 4489 patient records were audited. Documented completion rates for interventions ranged from 13% for ensuring a patient's tetanus vaccine is current to 97% of pregnant patients receiving the recommended prenatal vitamins. Electronic medical record-based needs assessments may provide a better basis for developing continuing medical education than a more traditional survey-based needs assessment. This electronic needs assessment uses the physician's own patient outcome information to assist in determining learning objectives that reflect both perceived and unperceived needs.

  14. ELF waves and ion resonances produced by an electron beam emitting rocket in the ionosphere

    International Nuclear Information System (INIS)

    Winckler, J.R.; Abe, Y.; Erickson, K.N.

    1986-01-01

    Results are reported from the ECHO-6 electron-beam-injection experiment, performed in the auroral-zone ionosphere on March 30, 1983 using a sounding rocket equipped with two electron guns and a free-flying plasma-diagnostics instrument package. The data are presented in extensive graphs and diagrams and characterized in detail. Large ELF wave variations, superposed on the strong beam-sector-directed quasi-dc component, are observed in the 100-eV beam-induced plasma when the beam is injected in a transverse spiral, but not when it is injected upward parallel to the magnetic-field line. ELF activity is found to be suppressed whenever the rocket passed through field lines with auroral activity, suggesting that the waves are produced by the interaction of the beam potentials, plasma currents, and return currents neutralizing the accelerator payload. 12 references

  15. A desktop 3D printer with dual extruders to produce customised electronic circuitry

    Science.gov (United States)

    Butt, Javaid; Onimowo, Dominic Adaoiza; Gohrabian, Mohammed; Sharma, Tinku; Shirvani, Hassan

    2018-03-01

    3D printing has opened new horizons for the manufacturing industry in general, and 3D printers have become the tools for technological advancements. There is a huge divide between the pricing of industrial and desktop 3D printers with the former being on the expensive side capable of producing excellent quality products and latter being on the low-cost side with moderate quality results. However, there is a larger room for improvements and enhancements for the desktop systems as compared to the industrial ones. In this paper, a desktop 3D printer called Prusa Mendel i2 has been modified and integrated with an additional extruder so that the system can work with dual extruders and produce bespoke electronic circuits. The communication between the two extruders has been established by making use of the In-Chip Serial Programming port on the Arduino Uno controlling the printer. The biggest challenge is to control the flow of electric paint (to be dispensed by the new extruder) and CFD (Computational Fluid Dynamics) analysis has been carried out to ascertain the optimal conditions for proper dispensing. The final product is a customised electronic circuit with the base of plastic (from the 3D printer's extruder) and electronic paint (from the additional extruder) properly dispensed to create a live circuit on a plastic platform. This low-cost enhancement to a desktop 3D printer can provide a new prospect to produce multiple material parts where the additional extruder can be filled with any material that can be properly dispensed from its nozzle.

  16. Biomolecular electrostatics and solvation: a computational perspective.

    Science.gov (United States)

    Ren, Pengyu; Chun, Jaehun; Thomas, Dennis G; Schnieders, Michael J; Marucho, Marcelo; Zhang, Jiajing; Baker, Nathan A

    2012-11-01

    An understanding of molecular interactions is essential for insight into biological systems at the molecular scale. Among the various components of molecular interactions, electrostatics are of special importance because of their long-range nature and their influence on polar or charged molecules, including water, aqueous ions, proteins, nucleic acids, carbohydrates, and membrane lipids. In particular, robust models of electrostatic interactions are essential for understanding the solvation properties of biomolecules and the effects of solvation upon biomolecular folding, binding, enzyme catalysis, and dynamics. Electrostatics, therefore, are of central importance to understanding biomolecular structure and modeling interactions within and among biological molecules. This review discusses the solvation of biomolecules with a computational biophysics view toward describing the phenomenon. While our main focus lies on the computational aspect of the models, we provide an overview of the basic elements of biomolecular solvation (e.g. solvent structure, polarization, ion binding, and non-polar behavior) in order to provide a background to understand the different types of solvation models.

  17. Pulse radiolysis of liquid water using picosecond electron pulses produced by a table-top terawatt laser system

    International Nuclear Information System (INIS)

    Saleh, Ned; Flippo, Kirk; Nemoto, Koshichi; Umstadter, Donald; Crowell, Robert A.; Jonah, Charles D.; Trifunac, Alexander D.

    2000-01-01

    A laser based electron generator is shown, for the first time, to produce sufficient charge to conduct time resolved investigations of radiation induced chemical events. Electron pulses generated by focussing terawatt laser pulses into a supersonic helium gas jet are used to ionize liquid water. The decay of the hydrated electrons produced by the ionizing electron pulses is monitored with 0.3 μs time resolution. Hydrated electron concentrations as high as 22 μM were generated. The results show that terawatt lasers offer both an alternative to linear accelerators and a means to achieve subpicosecond time resolution for pulse radiolysis studies. (c) 2000 American Institute of Physics

  18. Correlation of displacement effects produced by electrons, protons, and neutrons in silicon

    International Nuclear Information System (INIS)

    van Lint, V.A.J.; Gigas, G.; Barengoltz, J.

    1975-01-01

    The correlation of displacement effects produced by electrons, protons, and neutrons in silicon is studied. Available data from the literature is employed. In particular the scope of the study is limited to the degradation of excess carrier lifetime and device electrical parameters directly related to it. The degree to which displacement effects may be correlated in order to predict semiconductor device response based on response data to another type of radiation is discussed. Useful ranges of the correlation factors (K/sub tau/ ratios) as a function of device majority carrier type, device resistivity, and injection level are presented. A significant dependence on injection level for the correlation factors is found

  19. Properties of Silicon Dioxide Amorphous Nanopowder Produced by Pulsed Electron Beam Evaporation

    Directory of Open Access Journals (Sweden)

    Vladislav G. Il’ves

    2015-01-01

    Full Text Available SiO2 amorphous nanopowder (NP is produced with the specific surface area of 154 m2/g by means of evaporation by a pulsed electron beam aimed at Aerosil 90 pyrogenic amorphous NP (90 m2/g as a target. SiO2 NP nanoparticles showed improved magnetic, thermal, and optical properties in comparison to Aerosil 90 NP. Possible reasons of emergence of d0 ferromagnetism at the room temperature in SiO2 amorphous NP are discussed. Photoluminescent and cathode luminescent properties of the SiO2 NP were investigated.

  20. Beam diagnostics using transition radiation produced by a 100 Mev electron beam

    International Nuclear Information System (INIS)

    Jablonka, M.; Leroy, J.; Hanus, X.; Derost, J.C.; Wartski, L.

    1991-01-01

    We report on several experiments using the optical transition radiation (OTR) produced by a 100 MeV electron beam. In using a sensitive video camera coupled with a digital image processing system an accurate and simple beam profile monitor has been devised. In measuring with a photo-multiplier the radiation emitted in a small solid angle around the direction of the OTR emission, a signal very sensitive to beam energy variations has been obtained. These experiments have been carried out on the Saclay ALS linac

  1. Kinetic magnetization by fast electrons in laser-produced plasmas at sub-relativistic intensities

    Czech Academy of Sciences Publication Activity Database

    Pisarczyk, T.; Gus'kov, S. Yu.; Chodukowski, T.; Dudžák, Roman; Korneev, Ph.; Demchenko, N. N.; Kalinowska, Z.; Dostál, Jan; Zaras-Szydlowska, A.; Borodziuk, S.; Juha, Libor; Cikhardt, Jakub; Krása, Josef; Klír, Daniel; Cikhardtová, B.; Kubeš, P.; Krouský, Eduard; Krůs, Miroslav; Ullschmied, Jiří; Jungwirth, Karel; Hřebíček, Jan; Medřík, Tomáš; Golasowski, Jiří; Pfeifer, Miroslav; Renner, Oldřich; Singh, Sushil K.; Kar, S.; Ahmed, H.; Skála, Jiří; Pisarczyk, P.

    2017-01-01

    Roč. 24, č. 10 (2017), s. 1-11, č. článku 102711. ISSN 1070-664X R&D Projects: GA MŠk EF15_008/0000162 EU Projects: European Commission(XE) 654148 - LASERLAB-EUROPE Grant - others:ELI Beamlines(XE) CZ.02.1.01/0.0/0.0/15_008/0000162 Institutional support: RVO:68378271 ; RVO:61389021 Keywords : laser-produced plasma * femtosecond polaro-interferometry * spontaneous magnetic fiel * spatial and temporal electron density distribution Subject RIV: BL - Plasma and Gas Discharge Physics OBOR OECD: Fluids and plasma physics (including surface physics) Impact factor: 2.115, year: 2016

  2. Metallographic techniques for evaluation of Thermal Barrier Coatings produced by Electron Beam Physical Vapor Deposition

    International Nuclear Information System (INIS)

    Kelly, Matthew; Singh, Jogender; Todd, Judith; Copley, Steven; Wolfe, Douglas

    2008-01-01

    Thermal Barrier Coatings (TBC) produced by Electron Beam Physical Vapor Deposition (EB-PVD) are primarily applied to critical hot section turbine components. EB-PVD TBC for turbine applications exhibit a complicated structure of porous ceramic columns separated by voids that offers mechanical compliance. Currently there are no standard evaluation methods for evaluating EB-PVD TBC structure quantitatively. This paper proposes a metallographic method for preparing samples and evaluating techniques to quantitatively measure structure. TBC samples were produced and evaluated with the proposed metallographic technique and digital image analysis for columnar grain size and relative intercolumnar porosity. Incorporation of the proposed evaluation technique will increase knowledge of the relation between processing parameters and material properties by incorporating a structural link. Application of this evaluation method will directly benefit areas of quality control, microstructural model development, and reduced development time for process scaling

  3. 6,6'-Dimethoxygossypol: molecular structure, crystal polymorphism, and solvate formation

    Science.gov (United States)

    6,6´-Dimethoxygossypol (DMG) is a naturally produced derivative of gossypol that is found in relatively high concentration in some Gossypium barbadense cotton varieties. Like gossypol, DMG forms an equimolar solvate with acetic acid, but it was not clear if, like gossypol, the compound would form c...

  4. The charge-asymmetric nonlocally determined local-electric (CANDLE) solvation model

    Energy Technology Data Exchange (ETDEWEB)

    Sundararaman, Ravishankar; Goddard, William A. [Joint Center for Artificial Photosynthesis, Pasadena, California 91125 (United States)

    2015-02-14

    Many important applications of electronic structure methods involve molecules or solid surfaces in a solvent medium. Since explicit treatment of the solvent in such methods is usually not practical, calculations often employ continuum solvation models to approximate the effect of the solvent. Previous solvation models either involve a parametrization based on atomic radii, which limits the class of applicable solutes, or based on solute electron density, which is more general but less accurate, especially for charged systems. We develop an accurate and general solvation model that includes a cavity that is a nonlocal functional of both solute electron density and potential, local dielectric response on this nonlocally determined cavity, and nonlocal approximations to the cavity-formation and dispersion energies. The dependence of the cavity on the solute potential enables an explicit treatment of the solvent charge asymmetry. With four parameters per solvent, this “CANDLE” model simultaneously reproduces solvation energies of large datasets of neutral molecules, cations, and anions with a mean absolute error of 1.8 kcal/mol in water and 3.0 kcal/mol in acetonitrile.

  5. Application of backscatter electrons for large area imaging of cavities produced by neutron irradiation

    Energy Technology Data Exchange (ETDEWEB)

    Pastukhov, V.I. [Joint Stock Company “Institute of Nuclear Materials” (JSC “INM”), Zarechny, Sverdlovsk Region (Russian Federation); Ural Federal University Named After the First President of Russia, B. N. Yeltsyn, Ekaterinburg (Russian Federation); National Research Nuclear University MEPhI (Moscow Engineering Physics Institute), Moscow (Russian Federation); Averin, S.A.; Panchenko, V.L. [Joint Stock Company “Institute of Nuclear Materials” (JSC “INM”), Zarechny, Sverdlovsk Region (Russian Federation); National Research Nuclear University MEPhI (Moscow Engineering Physics Institute), Moscow (Russian Federation); Portnykh, I.A. [Joint Stock Company “Institute of Nuclear Materials” (JSC “INM”), Zarechny, Sverdlovsk Region (Russian Federation); Freyer, P.D. [Westinghouse Electric Company, Pittsburgh, PA (United States); Giannuzzi, L.A. [L.A. Giannuzzi & Associates LLC, Fort Myers, FL (United States); Garner, F.A., E-mail: frank.garner@dslextreme.com [National Research Nuclear University MEPhI (Moscow Engineering Physics Institute), Moscow (Russian Federation); Radiation Effects Consulting LLC, Richland, WA (United States); Texas A& M University, College Station, TX (United States)

    2016-11-15

    It is shown that with proper optimization, backscattered electrons in a scanning electron microscope can produce images of cavity distribution in austenitic steels over a large specimen surface for a depth of ∼500–700 nm, eliminating the need for electropolishing or multiple specimen production. This technique is especially useful for quantifying cavity structures when the specimen is known or suspected to contain very heterogeneous distributions of cavities. Examples are shown for cold-worked EK-164, a very heterogeneously-swelling Russian fast reactor fuel cladding steel and also for AISI 304, a homogeneously-swelling Western steel used for major structural components of light water cooled reactors. This non-destructive overview method of quantifying cavity distribution can be used to direct the location and number of required focused ion beam prepared transmission electron microscopy specimens for examination of either neutron or ion-irradiated specimens. This technique can also be applied in stereo mode to quantify the depth dependence of cavity distributions.

  6. Kinetic-energy distributions of O- produced by dissociative electron attachment to physisorbed O2

    International Nuclear Information System (INIS)

    Huels, M.A.; Parenteau, L.; Michaud, M.; Sanche, L.

    1995-01-01

    We report measurements of the kinetic energy (E k ) distributions of O - produced by low-energy electron impact (5.5--19.5 eV) on disordered multilayers of O 2 physisorbed on a polycrystalline Pt substrate. The results confirm that dissociative electron attachment (DEA) proceeds via the formation of the 2 Π u , 2 Σ g + (I), and 2 Σ x + (II) (x=g and/or u) states of O 2 -* . We also find evidence for an additional resonance, namely the 2 Σ u + (I), positioned at about 10 eV above the neutral ground state in the Franck-Condon region, and dissociating into O - +O( 3 P). The measurements suggest that the autodetachment lifetimes of the 2 Σ u + (I) and 2 Σ g + (II) states may be longer than previously suggested. It is also observed that the effects of electron energy loss (EEL) in the solid prior to DEA, O - scattering in the solid after dissociation, and the charge-induced polarization energy of the solid, broaden the E k distributions, shift them to lower anion energies, and result in additional structure in them. The effects of EEL on the desorption dynamics of O - are estimated from high-resolution electron-energy-loss spectra and excitation functions for losses in the vicinity of the Schumann-Runge continuum of the physisorbed O 2 molecules. We find indications for an enhancement of the optically forbidden X 3 Σ g - →A 3 Σ u + transition, and observe that the gas-phase Rydberg bands, for energy losses above 7 eV, are not distinguishable in the condensed phase

  7. Monte Carlo method for calculating the radiation skyshine produced by electron accelerators

    Energy Technology Data Exchange (ETDEWEB)

    Kong Chaocheng [Department of Engineering Physics, Tsinghua University Beijing 100084 (China)]. E-mail: kongchaocheng@tsinghua.org.cn; Li Quanfeng [Department of Engineering Physics, Tsinghua University Beijing 100084 (China); Chen Huaibi [Department of Engineering Physics, Tsinghua University Beijing 100084 (China); Du Taibin [Department of Engineering Physics, Tsinghua University Beijing 100084 (China); Cheng Cheng [Department of Engineering Physics, Tsinghua University Beijing 100084 (China); Tang Chuanxiang [Department of Engineering Physics, Tsinghua University Beijing 100084 (China); Zhu Li [Laboratory of Radiation and Environmental Protection, Tsinghua University, Beijing 100084 (China); Zhang Hui [Laboratory of Radiation and Environmental Protection, Tsinghua University, Beijing 100084 (China); Pei Zhigang [Laboratory of Radiation and Environmental Protection, Tsinghua University, Beijing 100084 (China); Ming Shenjin [Laboratory of Radiation and Environmental Protection, Tsinghua University, Beijing 100084 (China)

    2005-06-01

    Using the MCNP4C Monte Carlo code, the X-ray skyshine produced by 9 MeV, 15 MeV and 21 MeV electron linear accelerators were calculated respectively with a new two-step method combined with the split and roulette variance reduction technique. Results of the Monte Carlo simulation, the empirical formulas used for skyshine calculation and the dose measurements were analyzed and compared. In conclusion, the skyshine dose measurements agreed reasonably with the results computed by the Monte Carlo method, but deviated from computational results given by empirical formulas. The effect on skyshine dose caused by different structures of accelerator head is also discussed in this paper.

  8. The defects produced by electron irradiation in tellurium-doped germanium

    International Nuclear Information System (INIS)

    Fukuoka, Noboru; Saito, Haruo

    1989-01-01

    The nature of the irradiation induced defects in a germanium single crystal doped with tellurium was studied by DLTS and electrical measurements. The E c -0.21 eV level produced by irradiation with 1.5 MeV electrons was studied using the DLTS technique. It was found that the defect associated with this level is a divacancy. The E-center like defect (group V impurity-vacancy pair) introduces the E c -0.20 eV level in samples doped with a group V impurity. The level introduced by a tellurium (group VI impurity)-vacancy pair is deeper. The E c -0.16 eV level was generated by annealing at 430 K. A tellurium-vacancies complex is proposed as the defect associated with this level. (author)

  9. Solvated protein-DNA docking using HADDOCK

    Energy Technology Data Exchange (ETDEWEB)

    Dijk, Marc van; Visscher, Koen M.; Kastritis, Panagiotis L.; Bonvin, Alexandre M. J. J., E-mail: a.m.j.j.bonvin@uu.nl [Utrecht University, Bijvoet Center for Biomolecular Research, Faculty of Science-Chemistry (Netherlands)

    2013-05-15

    Interfacial water molecules play an important role in many aspects of protein-DNA specificity and recognition. Yet they have been mostly neglected in the computational modeling of these complexes. We present here a solvated docking protocol that allows explicit inclusion of water molecules in the docking of protein-DNA complexes and demonstrate its feasibility on a benchmark of 30 high-resolution protein-DNA complexes containing crystallographically-determined water molecules at their interfaces. Our protocol is capable of reproducing the solvation pattern at the interface and recovers hydrogen-bonded water-mediated contacts in many of the benchmark cases. Solvated docking leads to an overall improvement in the quality of the generated protein-DNA models for cases with limited conformational change of the partners upon complex formation. The applicability of this approach is demonstrated on real cases by docking a representative set of 6 complexes using unbound protein coordinates, model-built DNA and knowledge-based restraints. As HADDOCK supports the inclusion of a variety of NMR restraints, solvated docking is also applicable for NMR-based structure calculations of protein-DNA complexes.

  10. Solvated protein–DNA docking using HADDOCK

    International Nuclear Information System (INIS)

    Dijk, Marc van; Visscher, Koen M.; Kastritis, Panagiotis L.; Bonvin, Alexandre M. J. J.

    2013-01-01

    Interfacial water molecules play an important role in many aspects of protein–DNA specificity and recognition. Yet they have been mostly neglected in the computational modeling of these complexes. We present here a solvated docking protocol that allows explicit inclusion of water molecules in the docking of protein–DNA complexes and demonstrate its feasibility on a benchmark of 30 high-resolution protein–DNA complexes containing crystallographically-determined water molecules at their interfaces. Our protocol is capable of reproducing the solvation pattern at the interface and recovers hydrogen-bonded water-mediated contacts in many of the benchmark cases. Solvated docking leads to an overall improvement in the quality of the generated protein–DNA models for cases with limited conformational change of the partners upon complex formation. The applicability of this approach is demonstrated on real cases by docking a representative set of 6 complexes using unbound protein coordinates, model-built DNA and knowledge-based restraints. As HADDOCK supports the inclusion of a variety of NMR restraints, solvated docking is also applicable for NMR-based structure calculations of protein–DNA complexes.

  11. Solvated protein-DNA docking using HADDOCK

    NARCIS (Netherlands)

    van Dijk, Marc; Visscher, Koen M; Bonvin, Alexandre M.J.J; Kastritis, Panagiotis L.

    2013-01-01

    Interfacial water molecules play an important role in many aspects of protein-DNA specificity and recognition. Yet they have been mostly neglected in the computational modeling of these complexes. We present here a solvated docking protocol that allows explicit inclusion of water molecules in the

  12. Coupled-Multiplier Accelerator Produces High-Power Electron Beams for Industrial Applications

    International Nuclear Information System (INIS)

    Hatridge, M.; McIntyre, P.; Roberson, S.; Sattarov, A.; Thomas, E.; Meitzler, Charles

    2003-01-01

    The coupled multiplier is a new approach to efficient generation of MeV d.c. power for accelerator applications. High voltage is produced by a series of modules, each of which consists of a high-power alternator, step-up transformer, and 3-phase multiplier circuit. The alternators are connected mechanically along a rotating shaft, and connected by insulating flexible couplers. This approach differs from all previous d.c. technologies in that power is delivered to the various stages of the system mechanically, rather than through capacitive or inductive electrical coupling. For this reason the capital cost depends linearly on required voltage and power, rather than quadratically as with conventional technologies. The CM technology enables multiple electron beams to be driven within a common supply and insulating housing. MeV electron beam is extremely effective in decomposing organic contaminants in water. A 1 MeV, 100 kW industrial accelerator using the CM technology has been built and is being installed for treatment of wastewater at a petrochemical plant

  13. Partial solvation parameters and LSER molecular descriptors

    International Nuclear Information System (INIS)

    Panayiotou, Costas

    2012-01-01

    Graphical abstract: The one-to-one correspondence of LSER molecular descriptors and partial solvation parameters (PSPs) for propionic acid. Highlights: ► Quantum-mechanics based development of a new QSPR predictive method. ► One-to-one correspondence of partial solvation parameters and LSER molecular descriptors. ► Development of alternative routes for the determination of partial solvation parameters and solubility parameters. ► Expansion and enhancement of solubility parameter approach. - Abstract: The partial solvation parameters (PSP) have been defined recently, on the basis of the insight derived from modern quantum chemical calculations, in an effort to overcome some of the inherent restrictions of the original definition of solubility parameter and expand its range of applications. The present work continues along these lines and introduces two new solvation parameters, the van der Waals and the polarity/refractivity ones, which may replace both of the former dispersion and polar PSPs. Thus, one may use either the former scheme of PSPs (dispersion, polar, acidic, and basic) or, equivalently, the new scheme (van der Waals, polarity/refractivity, acidic, basic). The new definitions are made in a simple and straightforward manner and, thus, the strength and appeal of the widely accepted concept of solubility parameter is preserved. The inter-relations of the various PSPs are critically discussed and their values are tabulated for a variety of common substances. The advantage of the new scheme of PSPs is the bridge that makes with the corresponding Abraham’s LSER descriptors. With this bridge, one may exchange information between PSPs, LSER experimental scales, and quantum mechanics calculations such as via the COSMO-RS theory. The proposed scheme is a predictive one and it is applicable to, both, homo-solvated and hetero-solvated compounds. The new scheme is tested for the calculation of activity coefficients at infinite dilution, for octanol

  14. Advanced dielectric continuum model of preferential solvation

    Science.gov (United States)

    Basilevsky, Mikhail; Odinokov, Alexey; Nikitina, Ekaterina; Grigoriev, Fedor; Petrov, Nikolai; Alfimov, Mikhail

    2009-01-01

    A continuum model for solvation effects in binary solvent mixtures is formulated in terms of the density functional theory. The presence of two variables, namely, the dimensionless solvent composition y and the dimensionless total solvent density z, is an essential feature of binary systems. Their coupling, hidden in the structure of the local dielectric permittivity function, is postulated at the phenomenological level. Local equilibrium conditions are derived by a variation in the free energy functional expressed in terms of the composition and density variables. They appear as a pair of coupled equations defining y and z as spatial distributions. We consider the simplest spherically symmetric case of the Born-type ion immersed in the benzene/dimethylsulfoxide (DMSO) solvent mixture. The profiles of y(R ) and z(R ) along the radius R, which measures the distance from the ion center, are found in molecular dynamics (MD) simulations. It is shown that for a given solute ion z(R ) does not depend significantly on the composition variable y. A simplified solution is then obtained by inserting z(R ), found in the MD simulation for the pure DMSO, in the single equation which defines y(R ). In this way composition dependences of the main solvation effects are investigated. The local density augmentation appears as a peak of z(R ) at the ion boundary. It is responsible for the fine solvation effects missing when the ordinary solvation theories, in which z =1, are applied. These phenomena, studied for negative ions, reproduce consistently the simulation results. For positive ions the simulation shows that z ≫1 (z =5-6 at the maximum of the z peak), which means that an extremely dense solvation shell is formed. In such a situation the continuum description fails to be valid within a consistent parametrization.

  15. Sensorial analysis and electronic aroma detection to compare olive oils produced by different extraction methods

    Directory of Open Access Journals (Sweden)

    Vaz Freire, L. T.

    2011-12-01

    Full Text Available A sensorial analysis and an aroma analysis by electronic sensory devices were used to compare olive oils produced according to two different extraction methods. The extraction methods compared were the press system and two phase decanter. Samples were taken from the harvests of 2002-2004 and the olives were all from the same variety. The variety used was the Portuguese Galega sp. Olives were picked and technologically handled under predetermined and supervised conditions. Olive oils produced were better classified when the sensory analysis by a panel was applied than when an electronic sensory analysis was performed, even after sensor optimization. This observation is in accordance with the fact that olive oil has a low volatility matrix and “flavor”, rather than aroma, can give a clearer characterization than electronic sensory analysis alone, where aroma is the main characteristic evaluated.

    El análisis sensorial y el análisis de aromas por medio de sistemas sensoriales electrónicos han sido utilizado para comparar aceites de oliva producidos a través de dos sistemas de extracción diferentes. Los métodos de extracción comparados han sido el sistema de prensas y el decantador de dos fases. Las muestras fueron producidas durante las cosechas del periodo 2002- 2004, y las aceitunas eran todas de la misma variedad portuguesa Gallega sp. Las aceitunas fueron seleccionadas y tratadas tecnológicamente bajo condiciones predeterminadas y supervisadas. Los aceites producidos resultaron mejor clasificados cuando fue aplicado el análisis sensorial por panel que cuando se utilizó el análisis con detección electrónica de aromas, incluso después de la optimización de los sensores. Esta observación está de acuerdo con el hecho de que los aceites son una matriz poco volátil y que es el “flavour”, más que el aroma, el que junto con el gusto puede proporcionar una caracterización mejor que la detección electrónica, en

  16. Robe Development for Electrical Conductivity Analysis in an Electron Gun Produced Helium Plasma

    Science.gov (United States)

    Bragg-Sitton, Shannon M.; Bitteker, Leo; Rodgers, Stephen L. (Technical Monitor)

    2002-01-01

    The use of magnetohydrodynamic (MHD) power conversion systems, potentially coupled with a fission power source, is currently being investigated as a driver for an advanced propulsion system, such as a plasma thruster. The efficiency of a MHD generator is strongly dependent on the electrical conductivity of the fluid that passes through the generator; power density increases as fluid conductivity increases. Although traditional MHD flows depend on thermal ionization to enhance the electrical conductivity, ionization due to nuclear interactions may achieve a comparable or improved conductivity enhancement while avoiding many of the limitations inherent to thermal ionization. Calculations suggest that nuclear-enhanced electrical conductivity increases as the neutron flux increases; conductivity of pure He-3 greater than 10 mho/m may be achievable if exposed to a flux greater than 10(exp 12) neutrons/cm2/s.) However, this remains to be demonstrated experimentally. An experimental facility has been constructed at the Propulsion Research Center at the NASA Marshall Space Flight Center, using helium as the test fluid. High energy electrons will be used to simulate the effects of neutron-induced ionization of helium gas to produce a plasma. These experiments will be focused on diagnosis of the plasma in a virtually static system; results will be applied to future tests with a MHD system. Initial experiments will utilize a 50 keV electron gun that can operate at up to a current of 200 micro A. Spreading the electron beam over a four inch diameter window results in an electron flux of 1.5x 10(exp 13) e/sq cm/s. The equivalent neutron flux that would produce the same ionization fraction in helium is 1x10(exp 12) n/sq cm/s. Experiments will simulate the neutron generated plasma modeled by Bitteker, which takes into account the products of thermal neutron absorption in He-3, and includes various ion species in estimating the conductivity of the resulting plasma. Several

  17. Characterization of Ti-6Al-4V produced via electron beam additive manufacturing

    Science.gov (United States)

    Hayes, Brian J.

    In recent years, additive manufacturing (AM) has become an increasingly promising method used for the production of structural metallic components. There are a number of reasons why AM methods are attractive, including the ability to produce complex geometries into a near-net shape and the rapid transition from design to production. Ti-6Al-4V is a titanium alloy frequently used in the aerospace industry which is receiving considerable attention as a good candidate for processing via electron beam additive manufacturing (EBAM). The Sciaky EBAM method combines a high-powered electron beam, weld-wire feedstock, and a large build chamber, enabling the production of large structural components. In order to gain wide acceptance of EBAM of Ti-6Al-4V as a viable manufacturing method, it is important to understand broadly the microstructural features that are present in large-scale depositions, including specifically: the morphology, distribution and texture of the phases present. To achieve such an understanding, stereological methods were used to populate a database quantifying key microstructural features in Ti-6Al-4V including volume fraction of phases, alpha lath width, colony scale factor, and volume fraction of basket weave type microstructure. Microstructural features unique to AM, such as elongated grains and banded structures, were also characterized. Hardness and tensile testing were conducted and the results were related to the microstructural morphology and sample orientation. Lastly, fractured surfaces and defects were investigated. The results of these activities provide insight into the process-structure-properties relationships found in EBAM processed Ti-6Al-4V.

  18. Angular distributions of atomic vapor stream produced by electron beam heating

    Energy Technology Data Exchange (ETDEWEB)

    Ohba, Hironori; Amekawa, Kazuhiro; Shibata, Takemasa [Japan Atomic Energy Research Inst., Tokai, Ibaraki (Japan). Tokai Research Establishment

    1997-03-01

    The angular distributions were measured as a function of deposition rate for aluminium, copper, gadolinium and cerium vapor stream produced by an electron beam gun with water-cooled copper crucible. The distributions were recorded on the mounted on a semicircular (120mm in radius) mask over the evaporation source. The measured distributions were able to be described by a simple cosine law, that is cos{sup n} {theta}, except for the case of extremely high evaporation rate with a porous material, where n is a rate-dependent beaming exponent, {theta} is the angle from the vertical. For many kinds of evaporants, it was confirmed that the beaming exponents increase continuously from unity to 3 or 4 with increasing deposition rate and are approximately proportional to R{sup 0.25} where R is the deposition rate. Moreover, it was found that the beaming exponents n are able to be expressed as n = {alpha} Kn{sub 0}{sup -0.25}, where Kn{sub 0}{sup -1} is the inverse of Knudsen number, which is defined by the mean free path of evaporated atoms and the evaporation spot size, and {alpha} is the constant. (author)

  19. Angular distributions of atomic vapor stream produced by electron beam heating

    International Nuclear Information System (INIS)

    Ohba, Hironori; Amekawa, Kazuhiro; Shibata, Takemasa

    1997-03-01

    The angular distributions were measured as a function of deposition rate for aluminium, copper, gadolinium and cerium vapor stream produced by an electron beam gun with water-cooled copper crucible. The distributions were recorded on the mounted on a semicircular (120mm in radius) mask over the evaporation source. The measured distributions were able to be described by a simple cosine law, that is cos n θ, except for the case of extremely high evaporation rate with a porous material, where n is a rate-dependent beaming exponent, θ is the angle from the vertical. For many kinds of evaporants, it was confirmed that the beaming exponents increase continuously from unity to 3 or 4 with increasing deposition rate and are approximately proportional to R 0.25 where R is the deposition rate. Moreover, it was found that the beaming exponents n are able to be expressed as n = α Kn 0 -0.25 , where Kn 0 -1 is the inverse of Knudsen number, which is defined by the mean free path of evaporated atoms and the evaporation spot size, and α is the constant. (author)

  20. Generalized Born Models of Macromolecular Solvation Effects

    Science.gov (United States)

    Bashford, Donald; Case, David A.

    2000-10-01

    It would often be useful in computer simulations to use a simple description of solvation effects, instead of explicitly representing the individual solvent molecules. Continuum dielectric models often work well in describing the thermodynamic aspects of aqueous solvation, and approximations to such models that avoid the need to solve the Poisson equation are attractive because of their computational efficiency. Here we give an overview of one such approximation, the generalized Born model, which is simple and fast enough to be used for molecular dynamics simulations of proteins and nucleic acids. We discuss its strengths and weaknesses, both for its fidelity to the underlying continuum model and for its ability to replace explicit consideration of solvent molecules in macromolecular simulations. We focus particularly on versions of the generalized Born model that have a pair-wise analytical form, and therefore fit most naturally into conventional molecular mechanics calculations.

  1. Preferential solvation: dividing surface vs excess numbers.

    Science.gov (United States)

    Shimizu, Seishi; Matubayasi, Nobuyuki

    2014-04-10

    How do osmolytes affect the conformation and configuration of supramolecular assembly, such as ion channel opening and actin polymerization? The key to the answer lies in the excess solvation numbers of water and osmolyte molecules; these numbers are determinable solely from experimental data, as guaranteed by the phase rule, as we show through the exact solution theory of Kirkwood and Buff (KB). The osmotic stress technique (OST), in contrast, purposes to yield alternative hydration numbers through the use of the dividing surface borrowed from the adsorption theory. However, we show (i) OST is equivalent, when it becomes exact, to the crowding effect in which the osmolyte exclusion dominates over hydration; (ii) crowding is not the universal driving force of the osmolyte effect (e.g., actin polymerization); (iii) the dividing surface for solvation is useful only for crowding, unlike in the adsorption theory which necessitates its use due to the phase rule. KB thus clarifies the true meaning and limitations of the older perspectives on preferential solvation (such as solvent binding models, crowding, and OST), and enables excess number determination without any further assumptions.

  2. Preferential Solvation of an Asymmetric Redox Molecule

    Energy Technology Data Exchange (ETDEWEB)

    Han, Kee Sung; Rajput, Nav Nidhi; Vijayakumar, M.; Wei, Xiaoliang; Wang, Wei; Hu, Jian Z.; Persson, Kristin A.; Mueller, Karl T.

    2016-12-15

    The fundamental correlations between inter-molecular interactions, solvation structure and functionality of electrolytes are in many cases unknown, particularly for multi-component liquid systems. In this work, we explore such correlations by investigating the complex interplay between solubility and solvation structure for the electrolyte system comprising N-(ferrocenylmethyl)-N,N-dimethyl-N-ethylammonium bistrifluoromethylsulfonimide (Fc1N112-TFSI) dissolved in a ternary carbonate solvent mixture using combined NMR relaxation and computational analyses. Probing the evolution of the solvent-solvent, ion-solvent and ion-ion interactions with an increase in solute concentration provides a molecular level understanding of the solubility limit of the Fc1N112-TFSI system. An increase in solute con-centration leads to pronounced Fc1N112-TFSI contact-ion pair formation by diminishing solvent-solvent and ion-solvent type interactions. At the solubility limit, the precipitation of solute is initiated through agglomeration of contact-ion pairs due to overlapping solvation shells.

  3. Wave–particle interactions in a resonant system of photons and ion-solvated water

    Energy Technology Data Exchange (ETDEWEB)

    Konishi, Eiji, E-mail: konishi.eiji.27c@st.kyoto-u.ac.jp

    2017-02-26

    Highlights: • We consider a QED model of rotating water molecules with ion solvation effects. • The equations of motion are cast in terms of a conventional free electron laser. • We offer a new quantum coherence mechanism induced by collective instability. - Abstract: We investigate a laser model for a resonant system of photons and ion cluster-solvated rotating water molecules in which ions in the cluster are identical and have very low, non-relativistic velocities and direction of motion parallel to a static electric field induced in a single direction. This model combines Dicke superradiation with wave–particle interaction. As the result, we find that the equations of motion of the system are expressed in terms of a conventional free electron laser system. This result leads to a mechanism for dynamical coherence, induced by collective instability in the wave–particle interaction.

  4. Free radicals produced by the oxidation of gallic acid: An electron paramagnetic resonance study

    Directory of Open Access Journals (Sweden)

    Wagner Brett A

    2010-08-01

    Full Text Available Abstract Background Gallic acid (3,4,5-trihydroxybenzoic acid is found in a wide variety of plants; it is extensively used in tanning, ink dyes, as well as in the manufacturing of paper. The gallate moiety is a key component of many functional phytochemicals. In this work electron paramagnetic spectroscopy (EPR was used to detect the free radicals generated by the air-oxidation of gallic acid. Results We found that gallic acid produces two different radicals as a function of pH. In the pH range between 7-10, the spectrum of the gallate free radical is a doublet of triplets (aH = 1.00 G, aH = 0.23 G, aH = 0.28 G. This is consistent with three hydrogens providing hyperfine splitting. However, in a more alkaline environment, pH >10, the hyperfine splitting pattern transforms into a 1:2:1 pattern (aH (2 = 1.07 G. Using D2O as a solvent, we demonstrate that the third hydrogen (i.e. aH = 0.28 G at lower pH is a slowly exchanging hydron, participating in hydrogen bonding with two oxygens in ortho position on the gallate ring. The pKa of this proton has been determined to be 10. Conclusions This simple and novel approach permitted the understanding of the prototropic equilibrium of the semiquinone radicals generated by gallic acid, a ubiquitous compound, allowing new insights into its oxidation and subsequent reactions.

  5. Conductometric determination of solvation numbers of alkali metal cations

    International Nuclear Information System (INIS)

    Fialkov, Yu.Ya.; Gorbachev, V.Yu.; Chumak, V.L.

    1997-01-01

    Theories describing the interrelation of ion mobility with their effective radii in solutions are considered. Possibility of using these theories for determination the solvation numbers n s of some ions is estimated. According to conductometric data values of n s are calculated for alkali metal ions in propylene carbonate. The data obtained are compared with solvation numbers determined with the use of entropies of ions solvation. Change of n s values within temperature range 273.15-323.15 K is considered. Using literature data the effect of crystallographic radii of cations and medium permittivity on the the values of solvation numbers of cations are analyzed. (author)

  6. Atomistic characterization of the active-site solvation dynamics of a model photocatalyst

    DEFF Research Database (Denmark)

    Brandt van Driel, Tim; Kjær, Kasper Skov; Hartsock, Robert W.

    2016-01-01

    The interactions between the reactive excited state of molecular photocatalysts and surrounding solvent dictate reaction mechanisms and pathways, but are not readily accessible to conventional optical spectroscopic techniques. Here we report an investigation of the structural and solvation dynami...... of the iridium atoms by the acetonitrile solvent and demonstrate the viability of using diffuse X-ray scattering at free-electron laser sources for studying the dynamics of photocatalysis....

  7. Solvation of o-hydroxybenzoic acid in pure and modified supercritical carbon dioxide, according to numerical modeling data

    Science.gov (United States)

    Antipova, M. L.; Gurina, D. L.; Odintsova, E. G.; Petrenko, V. E.

    2015-08-01

    The dissolution of an elementary fragment of crystal structure (an o-hydroxybenzoic acid ( o-HBA) dimer) in both pure and modified supercritical (SC) carbon dioxide by adding methanol (molar fraction, 0.035) at T = 318 K, ρ = 0.7 g/cm3 is simulated. Features of the solvation mechanism in each solvent are revealed. The solvation of o-HBA in pure SC CO2 is shown to occur via electron donor-acceptor interactions. o-HBA forms a solvate complex in modified SC CO2 through hydrogen bonds between the carboxyl group and methanol. The hydroxyl group of o-HBA participates in the formation of an intramolecular hydrogen bond, and not in interactions with the solvent. It is concluded that the o-HBA-methanol complex is a stable molecular structure, and its lifetime is one order of magnitude higher than those of other hydrogen bonds in fluids.

  8. Anisotropy in angular distributions of 238U fission fragments by photons, produced in high energy electron interaction with Si monocrystal

    International Nuclear Information System (INIS)

    Kasilov, V.I.; Lapin, N.N.

    1981-01-01

    An enhancement is detected under the angle of 90 deg in the fission fragment yield from 238 U nuclei produced by photons emitted by high-energy electrons passing through a silicon monocrystal. The results enable one to select the most optimal conditions to obtain maximal yields of nuclear particles [ru

  9. Relativistic Electrons Produced by Foreshock Disturbances Observed Upstream of Earth's Bow Shock

    Science.gov (United States)

    Wilson, L. B., III; Sibeck, D. G.; Turner, D. L.; Osmane, A.; Caprioli, D.; Angelopoulos, V.

    2016-01-01

    Charged particles can be reflected and accelerated by strong (i.e., high Mach number) astrophysical collisionless shock waves, streaming away to form a foreshock region in communication with the shock. Foreshocks are primarily populated by suprathermal ions that can generate foreshock disturbances-largescale (i.e., tens to thousands of thermal ion Larmor radii), transient (approximately 5-10 per day) structures. They have recently been found to accelerate ions to energies of several keV. Although electrons in Saturn's high Mach number (M > 40) bow shock can be accelerated to relativistic energies (nearly 1000 keV), it has hitherto been thought impossible to accelerate electrons beyond a few tens of keV at Earth's low Mach number (1 =M foreshock disturbances to energies up to at least approximately 300 keV. Although such energetic electrons have been previously observed, their presence has been attributed to escaping magnetospheric particles or solar events. These relativistic electrons are not associated with any solar or magnetospheric activity. Further, due to their relatively small Larmor radii (compared to magnetic gradient scale lengths) and large thermal speeds (compared to shock speeds), no known shock acceleration mechanism can energize thermal electrons up to relativistic energies. The discovery of relativistic electrons associated with foreshock structures commonly generated in astrophysical shocks could provide a new paradigm for electron injections and acceleration in collisionless plasmas.

  10. How electronic dynamics with Pauli exclusion produces Fermi-Dirac statistics.

    Science.gov (United States)

    Nguyen, Triet S; Nanguneri, Ravindra; Parkhill, John

    2015-04-07

    It is important that any dynamics method approaches the correct population distribution at long times. In this paper, we derive a one-body reduced density matrix dynamics for electrons in energetic contact with a bath. We obtain a remarkable equation of motion which shows that in order to reach equilibrium properly, rates of electron transitions depend on the density matrix. Even though the bath drives the electrons towards a Boltzmann distribution, hole blocking factors in our equation of motion cause the electronic populations to relax to a Fermi-Dirac distribution. These factors are an old concept, but we show how they can be derived with a combination of time-dependent perturbation theory and the extended normal ordering of Mukherjee and Kutzelnigg for a general electronic state. The resulting non-equilibrium kinetic equations generalize the usual Redfield theory to many-electron systems, while ensuring that the orbital occupations remain between zero and one. In numerical applications of our equations, we show that relaxation rates of molecules are not constant because of the blocking effect. Other applications to model atomic chains are also presented which highlight the importance of treating both dephasing and relaxation. Finally, we show how the bath localizes the electron density matrix.

  11. How electronic dynamics with Pauli exclusion produces Fermi-Dirac statistics

    International Nuclear Information System (INIS)

    Nguyen, Triet S.; Nanguneri, Ravindra; Parkhill, John

    2015-01-01

    It is important that any dynamics method approaches the correct population distribution at long times. In this paper, we derive a one-body reduced density matrix dynamics for electrons in energetic contact with a bath. We obtain a remarkable equation of motion which shows that in order to reach equilibrium properly, rates of electron transitions depend on the density matrix. Even though the bath drives the electrons towards a Boltzmann distribution, hole blocking factors in our equation of motion cause the electronic populations to relax to a Fermi-Dirac distribution. These factors are an old concept, but we show how they can be derived with a combination of time-dependent perturbation theory and the extended normal ordering of Mukherjee and Kutzelnigg for a general electronic state. The resulting non-equilibrium kinetic equations generalize the usual Redfield theory to many-electron systems, while ensuring that the orbital occupations remain between zero and one. In numerical applications of our equations, we show that relaxation rates of molecules are not constant because of the blocking effect. Other applications to model atomic chains are also presented which highlight the importance of treating both dephasing and relaxation. Finally, we show how the bath localizes the electron density matrix

  12. Nonpolar solvation dynamics for a nonpolar solute in room ...

    Indian Academy of Sciences (India)

    Sandipa Indra

    2018-01-30

    Jan 30, 2018 ... Keywords. Solvation dynamics; nonpolar solvation; ionic liquid; molecular dynamics; linear response theory. 1. ... J. Chem. Sci. (2018) 130:3 spectrum of the excited probe molecule for imida- .... Therefore, the solute and the RTIL ions interact only ... interval of 30 ps from a long equilibrium trajectory of dura-.

  13. Channeling effect in electronic spectra produced by grazing impact of fast protons on insulator surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Archubi, C D; Gravielle, M S, E-mail: archubi@iafe.uba.a, E-mail: msilvia@iafe.uba.a [Instituto de Astronomia y Fisica del Espacio, Casilla de Correo 67, Sucursal 28, 1428, Buenos Aires (Argentina)

    2009-11-01

    Electron emission due to grazing scattering of fast protons from LiF and KCl surfaces is studied under axial incidence conditions. The differential emission probability is calculated within a distorted-wave formalism, taking into account axial channeled trajectories. For different emission angles, electronic spectra for proton incidence along the two principal crystal axes ([100] and [110]) are compared with those corresponding to an impact velocity in a random direction, finding effects associated with the channeling conditions.

  14. Electron transport phenomena and dense plasmas produced by ultra-short pulse laser interaction

    International Nuclear Information System (INIS)

    More, R.M.

    1994-01-01

    Recent experiments with femtosecond lasers provide a test bed for theoretical ideas about electron processes in hot dense plasmas. We briefly review aspects of electron conduction theory likely to prove relevant to femtosecond laser absorption. We show that the Mott-Ioffe-Regel limit implies a maximum inverse bremsstrahlung absorption of about 50% at temperatures near the Fermi temperature. We also propose that sheath inverse bremsstrahlung leads to a minimum absorption of 7-10% at high laser intensity

  15. Abacavir methanol 2.5-solvate

    Directory of Open Access Journals (Sweden)

    Phuong-Truc T. Pham

    2009-08-01

    Full Text Available The structure of abacavir (systematic name: {(1S,4R-4-[2-amino-6-(cyclopropylamino-9H-purin-9-yl]cyclopent-2-en-1-yl}methanol, C14H18N6O·2.5CH3OH, consists of hydrogen-bonded ribbons which are further held together by additional hydrogen bonds involving the hydroxyl group and two N atoms on an adjacent purine. The asymmetric unit also contains 2.5 molecules of methanol solvate which were grossly disordered and were excluded using SQUEEZE subroutine in PLATON [Spek, (2009. Acta Cryst. D65, 148–155].

  16. Rotation and solvation of ammonium ion

    International Nuclear Information System (INIS)

    Perrin, C.L.; Gipe, R.K.

    1987-01-01

    From nitrogen-15 spin-lattice relaxation times and nuclear Overhauser enhancements, the rotational correlations time tau/sub c/ for 15 NH 4 + was determined in s series of solvents. Values of tau/sub c/ range from 0.46 to 20 picoseconds. The solvent dependent of tau/sub c/ cannot be explained in terms of solvent polarity, molecular dipole moment, solvent basicity, solvent dielectric relaxation, or solvent viscosity. The rapid rotation and the variation with solvent can be accounted for by a model that involves hydrogen bonding of an NH proton to more than one solvent molecule in a disordered solvation environment. 25 references, 1 table

  17. A Study of High Transverse Momentum Electrons Produced in pp Collisions at 540 GeV

    DEFF Research Database (Denmark)

    Bagnaia, P; Kofoed-Hansen, O.

    1984-01-01

    The production of electrons with very high transverse momentum has been studied in the UA2 experiment at the CERN [`(p)]ppp collider ( Öss =540 GeV). From a sample of events containing an electron candidate withp T >15 GeV/c, we extract a clear signal resulting from the production of the charged...... intermediate vector bosonW ±, which subsequently decays into an electron and a neutrino. We study theW production and decay properties. Further-more, we refine our results on the production and decay of the neutral vector bosonZ 0. Finally, we compare the experimental results to the predictions of the standard...

  18. Plasma conditions for non-Maxwellian electron distributions in high current discharges and laser-produced plasmas

    International Nuclear Information System (INIS)

    Whitney, K.G.; Pulsifer, P.E.

    1993-01-01

    Results from the standard quasilinear theory of ion-acoustic and Langmuir plasma microturbulence are incorporated into the kinetic theory of the electron distribution function. The theory is then applied to high current discharges and laser-produced plasmas, where either the current flow or the nonlinear laser-light absorption acts, respectively, as the energy source for the microturbulence. More specifically, the theory is applied to a selenium plasma, whose charge state is determined under conditions of collisional-radiative equilibrium, and plasma conditions are found under which microturbulence strongly influences the electron kinetics. In selenium, we show that this influence extends over a wide range of plasma conditions. For ion-acoustic turbulence, a criterion is derived, analogous to one previously obtained for laser heated plasmas, that predicts when Ohmic heating dominates over electron-electron collisions. This dominance leads to the generation of electron distributions with reduced high-energy tails relative to a Maxwellian distribution of the same temperature. Ion-acoustic turbulence lowers the current requirements needed to generate these distributions. When the laser heating criterion is rederived with ion-acoustic turbulence included in the theory, a similar reduction in the laser intensity needed to produce non-Maxwellian distributions is found. Thus we show that ion-acoustic turbulence uniformly (i.e., by the same numerical factor) reduces the electrical and heat conductivities, as well as the current (squared) and laser intensity levels needed to drive the plasma into non-Maxwellian states

  19. Consequences of the collision symmetry on the observed electron spectra produced by autoionisation

    International Nuclear Information System (INIS)

    Gleizes, A.; Bordenave-Montesquieu, A.; Benoit-Cattin, P.

    1980-01-01

    Some properties of symmetrical collisions observed in the decay of the helium autoionising states by electron emission are reported. They have been seen in the He + on He and the He on He collisional systems within the 7 to 140 keV energy range. Comparison of the excitation processes for the fast and slow atoms is made through the measurement of ejected-electron line shape and angular distributions for various autoionising states. At low energy the symmetry of the two systems is well verified; discrepancies from the symmetry requirements are observed in the angular distributions for the neutral-neutral system at high collision energy. (author)

  20. Structure and properties of parts produced by electron-beam additive manufacturing

    Science.gov (United States)

    Klimenov, Vasilii; Klopotov, Anatolii; Fedorov, Vasilii; Abzaev, Yurii; Batranin, Andrey; Kurgan, Kirill; Kairalapov, Daniyar

    2017-12-01

    The paper deals with the study of structure, microstructure, composition and microhardness of a tube processed by electron-beam additive manufacturing using optical and scanning electron microscopy. The structure and macrodefects of a tube made of Grade2 titanium alloy is studied using the X-ray computed tomography. The principles of layer-by-layer assembly and boundaries after powder sintering are set out in this paper. It is found that the titanium alloy has two phases. Future work will involve methods to improve properties of created parts.

  1. Study of radicals or radical ions formed by radiolysis of n-methylacetamide and of its mixtures with water and some organic solvents. Problem of solvation of electrons in structured media

    International Nuclear Information System (INIS)

    Tran-Thi, Thu-Hoa

    1978-01-01

    Based on two hypotheses (effect of structure, and electron affinity), and on the use of two complementary techniques (pulsed radiolysis and gamma radiolysis), this research thesis reports the study of the fate of primary species formed during the radiolysis of N-methylacetamide, either pure or mixed with other solvents. The author first presents experimental conditions, the experimental techniques and their results for both types of radiolysis, and then discusses these results

  2. Ab initio joint density-functional theory of solvated electrodes, with model and explicit solvation

    Science.gov (United States)

    Arias, Tomas

    2015-03-01

    First-principles guided design of improved electrochemical systems has the potential for great societal impact by making non-fossil-fuel systems economically viable. Potential applications include improvements in fuel-cells, solar-fuel systems (``artificial photosynthesis''), supercapacitors and batteries. Economical fuel-cell systems would enable zero-carbon footprint transportation, solar-fuel systems would directly convert sunlight and water into hydrogen fuel for such fuel-cell vehicles, supercapacitors would enable nearly full recovery of energy lost during vehicle braking thus extending electric vehicle range and acceptance, and economical high-capacity batteries would be central to mitigating the indeterminacy of renewable resources such as wind and solar. Central to the operation of all of the above electrochemical systems is the electrode-electrolyte interface, whose underlying physics is quite rich, yet remains remarkably poorly understood. The essential underlying technical challenge to the first principles studies which could explore this physics is the need to properly represent simultaneously both the interaction between electron-transfer events at the electrode, which demand a quantum mechanical description, and multiscale phenomena in the liquid environment such as the electrochemical double layer (ECDL) and its associated shielding, which demand a statistical description. A direct ab initio approach to this challenge would, in principle, require statistical sampling and thousands of repetitions of already computationally demanding quantum mechanical calculations. This talk will begin with a brief review of a recent advance, joint density-functional theory (JDFT), which allows for a fully rigorous and, in principle, exact representation of the thermodynamic equilibrium between a system described at the quantum-mechanical level and a liquid environment, but without the need for costly sampling. We then shall demonstrate how this approach applies in

  3. Confinement of hot, hard x-ray producing electrons in solar flares

    International Nuclear Information System (INIS)

    Smith, D.F.; Lilliequist, C.G.

    1979-01-01

    Possible thermal models for solar, hard X-ray emission, consisting of small volumes in which the electrons are rapidly heated to 4 x 10 8 K, are examined to determine under what conditions such models can be more efficient than nonthermal models. The primary energy-loss mechanism in these models is source expansion due to heat conduction which deviates from its classical value by mechanisms which are reviewed and systematized. One such mechanism is saturation of the heat flux at its maximum possible value, corresponding to direct convection by electrons. Another mechanism is anomalous limitation of the heat flux due to instability of the return current which must compensate the electron current carrying the heat. A simple, one-dimensional model in which a section of the flux tube of constant density is heated to 4 x 10 8 K is analyzed. A conduction front, determined by the above collisionless process, moves along the flux tube at the head of the expanding source. A more realistic, one-dimensional, one-fluid, two-temperature model with a spatially and temporally varying energy source which delivers energy to the electrons at a finite rate is formulated and solved numerically. This results in some ion heating and mass motions which, by themselves, represent only a small energy loss. However, because of changes in the anomalous limitation of the heat flux with higher ion temperature, the expansion losses increase considerably

  4. Electron-spin polarization of photoions produced through photoionization from the laser-excited triplet state of Sr

    International Nuclear Information System (INIS)

    Yonekura, Nobuaki; Nakajima, Takashi; Matsuo, Yukari; Kobayashi, Tohru; Fukuyama, Yoshimitsu

    2004-01-01

    We report the detailed experimental study on the production of electron-spin-polarized Sr + ions through one-photon resonant two-photon ionization via laser-excited 5s5p 3 P 1 (M J =+1) of Sr atoms produced by laser-ablation. We have experimentally confirmed that the use of laser-ablation for the production of Sr atoms prior to photoionization does not affect the electron-spin polarization. We have found that the degree of electron-spin polarization is 64±9%, which is in good agreement with our recent theoretical prediction. As we discuss in detail, we infer, from a simple analysis, that photoelectrons, being the counterpart of electron-spin-polarized Sr + ions, have approximately the same degree of electron-spin polarization. Our experimental results demonstrate that the combined use of laser-ablation technique and pulsed lasers for photoionization would be a compact and effective way to realize a pulsed source for spin-polarized ions and electrons for the studies of various spin-dependent dynamics in chemical physics

  5. Isochoric heating of reduced mass targets by ultra-intense laser produced relativistic electrons

    Energy Technology Data Exchange (ETDEWEB)

    Neumayer, P; Lee, H J; Offerman, D; Shipton, E; Kemp, A; Kritcher, A L; Doppner, T; Back, C A; Glenzer, S H

    2009-02-04

    We present measurements of the chlorine K-alpha emission from reduced mass targets, irradiated with ultra-high intensity laser pulses. Chlorinated plastic targets with diameters down to 50 micrometers and mass of a few 10{sup -8} g were irradiated with up to 7 J of laser energy focused to intensities of several 10{sup 19} W/cm{sup 2}. The conversion of laser energy to K-alpha radiation is measured, as well as high resolution spectra that allow observation of line shifts, indicating isochoric heating of the target up to 18 eV. A zero-dimensional 2-temperature equilibration model, combined with electron impact K-shell ionization and post processed spectra from collisional radiative calculations reproduces the observed K-alpha yields and line shifts, and shows the importance of target expansion due to the hot electron pressure.

  6. Electronic system for the automation of current measurements produced by ionization chambers

    International Nuclear Information System (INIS)

    Brancaccio, Franco; Dias, Mauro da Silva

    2002-01-01

    Ionization Chambers in current mode operation are usually used in Nuclear Metrology in the determination of radionuclide activity. For this purpose measurements of very low ionization currents, in the range of 10 -8 to 10 -14 A, are required. Usually, electrometers perform the current integration method under command of signals from an automation system, in order to reduce the measurement uncertainties. In the present work, an automation system, developed for current integration measurements at the Laboratorio de Metrologia Nuclear (LMN) of Instituto de Pesquisas Energeticas e Nucleares (IPEN), is described. This automation system is composed by software (graphic interface and control) and an electronic module connected to a microcomputer, by means of a commercial data acquisition card CAD12/32 (LYNX Tecnologia Eletronica Ltda.). Measurements, using an electrometer Keithley 616 (Keithley Instruments, Inc) and an ionization chamber IG12/A20 (20 th Century Electronics Ltd.), were performed in order to check the system and for validating the project. (author)

  7. Evaluation by electronic paramagnetic resonance of the number of free radicals produced in irradiated rat bone

    International Nuclear Information System (INIS)

    Marble, G.; Valderas, R.

    1966-01-01

    The number of long half-life free radicals created by gamma irradiation in the bones of the rat has been determined from the electrons paramagnetic resonance spectrum. This number decreases slowly with time (calculated half life: 24 days). It is proportional to the dose of gamma radiation given to the rat. The method could find interesting applications in the field of biological dosimetry. (authors) [fr

  8. Photoelectron linear accelerator for producing a low emittance polarized electron beam

    Science.gov (United States)

    Yu, David U.; Clendenin, James E.; Kirby, Robert E.

    2004-06-01

    A photoelectron linear accelerator for producing a low emittance polarized electric beam. The accelerator includes a tube having an inner wall, the inner tube wall being coated by a getter material. A portable, or demountable, cathode plug is mounted within said tube, the surface of said cathode having a semiconductor material formed thereon.

  9. Metallurgical Mechanisms Controlling Mechanical Properties of Aluminum Alloy 2219 Produced By Electron Beam Freeform Fabrication

    Science.gov (United States)

    Domack, Marcia S.; Taminger, Karen M. B.; Begley, Matthew

    2006-01-01

    The electron beam freeform fabrication (EBF3) layer-additive manufacturing process has been developed to directly fabricate complex geometry components. EBF3 introduces metal wire into a molten pool created on the surface of a substrate by a focused electron beam. Part geometry is achieved by translating the substrate with respect to the beam to build the part one layer at a time. Tensile properties have been demonstrated for electron beam deposited aluminum and titanium alloys that are comparable to wrought products, although the microstructures of the deposits exhibit features more typical of cast material. Understanding the metallurgical mechanisms controlling mechanical properties is essential to maximizing application of the EBF3 process. In the current study, mechanical properties and resulting microstructures were examined for aluminum alloy 2219 fabricated over a range of EBF3 process variables. Material performance was evaluated based on tensile properties and results were compared with properties of Al 2219 wrought products. Unique microstructures were observed within the deposited layers and at interlayer boundaries, which varied within the deposit height due to microstructural evolution associated with the complex thermal history experienced during subsequent layer deposition. Microstructures exhibited irregularly shaped grains, typically with interior dendritic structures, which were described based on overall grain size, morphology, distribution, and dendrite spacing, and were correlated with deposition parameters. Fracture features were compared with microstructural elements to define fracture paths and aid in definition of basic processing-microstructure-property correlations.

  10. On the idea of low-energy nuclear reactions in metallic lattices by producing neutrons from protons capturing "heavy" electrons

    Science.gov (United States)

    Tennfors, Einar

    2013-02-01

    The present article is a critical comment on Widom and Larsens speculations concerning low-energy nuclear reactions (LENR) based on spontaneous collective motion of protons in a room temperature metallic hydride lattice producing oscillating electric fields that renormalize the electron self-energy, adding significantly to the effective electron mass and enabling production of low-energy neutrons. The frequency and mean proton displacement estimated on the basis of neutron scattering from protons in palladium and applied to the Widom and Larsens model of the proton oscillations yield an electron mass enhancement less than one percent, far below the threshold for the proposed neutron production and even farther below the mass enhancement obtained by Widom and Larsen assuming a high charge density. Neutrons are not stopped by the Coulomb barrier, but the energy required for the neutron production is not low.

  11. Solvation of hydrocarbons in aqueous-organic mixtures

    International Nuclear Information System (INIS)

    Sedov, I.A.; Magsumov, T.I.; Solomonov, B.N.

    2016-01-01

    Highlights: • Thermodynamic functions of solvation in mixtures of water with acetone and acetonitrile are measured at T = 298.15 K. • Solvation of n-octane and toluene in aqueous-organic mixtures is studied. • When increasing water content, Gibbs free energies grow up steadily, while enthalpies have a maximum. • Hydrocarbons are preferentially solvated with organic cosolvent even in mixtures with rather high water content. • Acetonitrile suppresses the hydrophobic effect less than acetone. - Abstract: We study the solvation of two hydrocarbons, n-octane and toluene, in binary mixtures of water with organic cosolvents. Two polar aprotic cosolvents that are miscible with water in any proportions, acetonitrile and acetone, were considered. We determine the magnitudes of thermodynamic functions of dissolution and solvation at T = 298.15 K in the mixtures with various compositions. Solution calorimetry was used to measure the enthalpies of solution, and GC headspace analysis was applied to obtain limiting activity coefficients of solutes in the studied systems. For the first time, the enthalpies of solution of alkane in the mixtures with high water content were measured directly. We observed well-pronounced maxima of the dependencies of enthalpies of solvation from the composition of solvent and no maxima for the Gibbs free energies of solvation. Two factors are concluded to be important to explain the observed tendencies: high energy cost of reorganization of binary solvent upon insertion of solute molecules and preferential surrounding of hydrocarbons with the molecules of organic cosolvent. Enthalpy-entropy compensation leads to a steady growth of the Gibbs free energies with increasing water content. On the other hand, consideration of the plots of the Gibbs free energy against enthalpy of solvation clearly shows that the solvation properties are changed dramatically after addition of a rather small amount of organic cosolvents. It is shown that they

  12. Infrared spectroscopy of model electrochemical interfaces in ultrahigh vacuum: some implications for ionic and chemisorbate solvation at electrode surfaces

    Science.gov (United States)

    Villegas, Ignacio; Kizhakevariam, Naushad; Weaver, Michael J.

    1995-07-01

    The utility of infrared reflection-absorption spectroscopy (IRAS) for examining structure and bonding for model electrochemical interfaces in ultrahigh vacuum (UHV) is illustrated, focusing specifically on the solvation of cations and chemisorbed carbon monoxide on Pt(111). These systems were chosen partly in view of the availability of IRAS data (albeit limited to chemisorbate vibrations) for the corresponding in-situ metal-solution interfaces, enabling direct spectral comparisons to be made with the "UHV electrochemical model" systems. Kelvin probe measurements of the metal-UHV surface potential changes (ΔΦ) attending alterations in the interfacial composition are also described: these provide the required link to the in-situ electrode potentials as well as yielding additional insight into surface solvation. Variations in the negative electronic charge density and, correspondingly, in the cation surface concentration (thereby mimicking charge-induced alterations in the electrode potential below the potential of zero charge) are achieved by potassium atom dosage onto Pt(111). Of the solvents selected for discussion here — deuterated water, methanol, and acetonitrile — the first two exhibit readily detectable vibrational bands which provide information on the ionic solvation structure. Progressively dosing these solvents onto Pt(111) in the presence of low potassium coverages yields marked alterations in the solvent vibrational bands which can be understood in terms of sequential cation solvation. Comparison between these spectra for methanol with analogous data for sequential methanol solvation of gas-phase alkali cations enables the influence of the interfacial environment to be assessed. The effects of solvating chemisorbed CO are illustrated for acetonitrile; the markedly larger shifts in CO frequencies and binding sites for dilute CO adlayers can be accounted for in terms of short-range coadsorbate interactions in addition to longer-range Stark effects

  13. Fragmentation study of isolated and nano-solvated biomolecules induced by collision with multiply charged ions and neutral particles

    International Nuclear Information System (INIS)

    Bernigaud, V.

    2009-01-01

    This thesis concerns a gas phase study of the fragmentation of bio-molecular systems induced by slow collisions with multiply charged ions (in the keV-region), alkali atoms and rare gases. The main objective was to study the physical processes involved in the dissociation of highly electronically excited systems. In order to elucidate the intrinsic properties of certain biomolecules (porphyrins and amino acids) we have performed experiments in the gas phase with isolated systems. The obtained results demonstrate the high stability of porphyrins after electron removal and attachment. Furthermore, a dependence of the fragmentation pattern produced by multiply charged ions on the isomeric structure of the alanine molecule has been shown. In a second part of the thesis, a strong influence of the environment of the biomolecule on the fragmentation channels, their modification and their new opening, has been clearly proven. This phenomenon occurs in the presence of other surrounding biomolecules (clusters of nucleobases) as well as for molecules of a solvent (molecules of water, methanol and acetonitrile) in which the biomolecule is embedded. In order to extend these studies to larger systems, a new experimental set-up, based on an electro-spray ion source combined with a quadrupole mass filter has been developed. Due to the successful tests and proposed improvements of the device future experiments will become available concerning the fragmentation of large charged and solvated bio-molecular systems induced by collision processes. (author) [fr

  14. Transmission electron microscopy studies on nanometer-sized ω phase produced in Gum Metal

    International Nuclear Information System (INIS)

    Yano, Takaaki; Murakami, Yasukazu; Shindo, Daisuke; Hayasaka, Yuichiro; Kuramoto, Shigeru

    2010-01-01

    The morphology, numerical density and average spacing of the ω phase formed in Gum Metal, a Ti-based alloy showing unique mechanical properties, were studied by transmission electron microscopy. Based on dark-field image observations and precise thickness measurements using a thin-foil specimen, the average spacing of the nanometer-sized ω phase was determined to be 6 nm. This spacing appeared to be sufficiently small for trapping dislocations. The results are discussed in conjunction with the dislocation-free deformation mechanism proposed for Gum Metal.

  15. Solvation of lithium ion in dimethoxyethane and propylene carbonate

    Science.gov (United States)

    Chaban, Vitaly

    2015-07-01

    Solvation of the lithium ion (Li+) in dimethoxyethane (DME) and propylene carbonate (PC) is of scientific significance and urgency in the context of lithium-ion batteries. I report PM7-MD simulations on the composition of Li+ solvation shells (SH) in a few DME/PC mixtures. The equimolar mixture features preferential solvation by PC, in agreement with classical MD studies. However, one DME molecule is always present in the first SH, supplementing the cage formed by five PC molecules. As PC molecules get removed, DME gradually substitutes vacant places. In the PC-poor mixtures, an entire SH is populated by five DME molecules.

  16. Measurement of photon showers in lead produced by electrons of 150 MeV

    International Nuclear Information System (INIS)

    Goeringer, H.; Eyss, H.J. von; Schoch, B.

    1976-01-01

    The photon energy spectra induced by 150 MeV electrons in lead were measured in the energy range from 40 MeV up to the primary electron energy. The target thickness was varied between 0.1 and 2.5 radiation lengths X 0 . The photons were analyzed by use of a technique based on deuteron photodisintegration. Differential and integral shower spectra are presented and compared with Monte Carlo calculations of Nagel and Messel et al., both interpolated to our primary energy of 150 MeV. The measured spectra show good agreement with these Monte Carlo calculations for the thickest target of 2.5X 0 and with calculated bremsstrahlung spectra for the thinnest target of 0.1X 0 . Considerable discrepancies, however, are found for medium target thicknesses in the range 0 . Around the shower maxima, the shower spectra are narrower and the maxima are shifted about 0.3-0.4X 0 to lower target thicknesses, furthermore the number of photons at the shower maxima are up to 50% higher than calculated. (Auth.)

  17. IRIS , Hinode , SDO , and RHESSI Observations of a White Light Flare Produced Directly by Non-thermal Electrons

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Kyoung-Sun [Hinode Science Center, National Astronomical Observatory of Japan (NAOJ), 2-21-1, Osawa, Mitaka, Tokyo 181-8588 (Japan); Imada, Shinsuke [Institute for Space–Earth Environmental Research (ISEE), Nagoya University, Furo-cho, Chikusa-ku, Nagoya 466-8550 (Japan); Watanabe, Kyoko [National Defense Academy of Japan, 1-10-20 Hashirimizu, Yokosuka 239-8686 (Japan); Bamba, Yumi [Hinode team, ISAS/JAXA, 3-1-1 Yoshinodai, Chuo-ku, Sagamihara, Kanagawa 252-5210 (Japan); Brooks, David H., E-mail: ksun.lee@nao.ac.jp [College of Science, George Mason University, 4400 University Drive, Fairfax, VA 22030 (United States)

    2017-02-20

    An X1.6 flare occurred in active region AR 12192 on 2014 October 22 at 14:02 UT and was observed by Hinode , IRIS , SDO , and RHESSI . We analyze a bright kernel that produces a white light (WL) flare with continuum enhancement and a hard X-ray (HXR) peak. Taking advantage of the spectroscopic observations of IRIS and Hinode /EIS, we measure the temporal variation of the plasma properties in the bright kernel in the chromosphere and corona. We find that explosive evaporation was observed when the WL emission occurred, even though the intensity enhancement in hotter lines is quite weak. The temporal correlation of the WL emission, HXR peak, and evaporation flows indicates that the WL emission was produced by accelerated electrons. To understand the WL emission process, we calculated the energy flux deposited by non-thermal electrons (observed by RHESSI ) and compared it to the dissipated energy estimated from a chromospheric line (Mg ii triplet) observed by IRIS . The deposited energy flux from the non-thermal electrons is about (3–7.7) × 10{sup 10} erg cm{sup −2} s{sup −1} for a given low-energy cutoff of 30–40 keV, assuming the thick-target model. The energy flux estimated from the changes in temperature in the chromosphere measured using the Mg ii subordinate line is about (4.6–6.7) × 10{sup 9} erg cm{sup −2} s{sup −1}: ∼6%–22% of the deposited energy. This comparison of estimated energy fluxes implies that the continuum enhancement was directly produced by the non-thermal electrons.

  18. Retrograde amnesia produced by electron beam exposure: causal parameters and duration of memory loss

    International Nuclear Information System (INIS)

    Wheeler, T.G.; Hardy, K.A.

    1985-01-01

    The production of retrograde amnesia (RA) upon electron beam exposure has been investigated. RA production was evaluated using a single-trial avoidance task across a 10 4 dose range for 10-, 1-, and 0.1-μsec pulsed exposures. The dose-response curve obtained at each pulse duration showed significant RA production. The most effective dose range was 0.1-10 rad at a dose rate of 10 6 rad/sec. By employing a 10 rad (10 6 rad/sec) pulse, a memory loss of the events occurring in the previous 4 sec was demonstrated. The conclusion was that the RA effect might be due to sensory activation which provided a novel stimulus that masked previous stimuli

  19. Retrograde amnesia produced by electron beam exposure: causal parameters and duration of memory loss. [Rats

    Energy Technology Data Exchange (ETDEWEB)

    Wheeler, T.G.; Hardy, K.A.

    1985-01-01

    The production of retrograde amnesia (RA) upon electron beam exposure has been investigated. RA production was evaluated using a single-trial avoidance task across a 10/sup 4/ dose range for 10-, 1-, and 0.1-..mu..sec pulsed exposures. The dose-response curve obtained at each pulse duration showed significant RA production. The most effective dose range was 0.1-10 rad at a dose rate of 10/sup 6/ rad/sec. By employing a 10 rad (10/sup 6/ rad/sec) pulse, a memory loss of the events occurring in the previous 4 sec was demonstrated. The conclusion was that the RA effect might be due to sensory activation which provided a novel stimulus that masked previous stimuli.

  20. Parametric emittance measurements of electron beams produced by a laser plasma accelerator

    Science.gov (United States)

    Barber, S. K.; van Tilborg, J.; Schroeder, C. B.; Lehe, R.; Tsai, H.-E.; Swanson, K. K.; Steinke, S.; Nakamura, K.; Geddes, C. G. R.; Benedetti, C.; Esarey, E.; Leemans, W. P.

    2018-05-01

    Laser plasma accelerators (LPA) offer an exciting possibility to deliver high energy, high brightness electrons beams in drastically smaller distance scales than is typical for conventional accelerators. As such, LPAs draw considerable attention as potential drivers for next generation light sources and for a compact linear collider. In order to asses the viability of an LPA source for a particular application, the brightness of the source should be properly characterized. In this paper, we present charge dependent transverse emittance measurements of LPA sources using both ionization injection and shock induced density down ramp injection, with the latter delivering smaller transverse emittances by a factor of two when controlling for charge density. The single shot emittance method is described in detail with a discussion on limitations related to second order transport effects. The direct role of space charge is explored through a series of simulations and found to be consistent with experimental observations.

  1. Generation of EM radiations using intense electron beam produced in vacuum

    Energy Technology Data Exchange (ETDEWEB)

    Shukla, R.; Shyam, A.; Verma, R.; Deb, P.; Mishra, E.; Meena, M., E-mail: rshukla@barc.gov.in [Energetics and Electromagnetics Division, Bhabha Atomic Research Centre Facility, Visakhapatnam (India)

    2014-07-01

    The results of a pulse power generator driving an axial virtual cathode oscillator are being presented in this paper as a source of high power microwave (HPM) radiations. The electron beam generator is also modified to attain the intense X-ray burst. The pulse power generator used for these applications is common and is having 10 ohms as its characteristic impedance with 50nS of pulse width. The peak charging voltage of the pulse forming line is 450 kV and hence 225 kV and 22.5 kA is peak voltage and peak current delivery capabilities respectively for the pulse power generator. The peak electrical power of the generator is 5GW for a matched load. The charging power supply for the pulse forming line consists of a high voltage generator made by pulse transformer and charging the pulse forming line in the first cycle of the charging pulse. To utilize the energy of the primary capacitive storage efficiently the pulse transformer is having 0.8 coupling coefficient between its primary and the secondary. The axial vircator chamber is evacuated to attain the vacuum of 2 x 10{sup -4} torr for the HPM application. In the case of modified electron beam chamber for the generation of X-rays the vacuum of same order is used. The pulse forming line is made using equal lengths of high voltage transmission lines, each having a length of 10 meters, connected in the parallel to give a net source impedance of 10 ohm. The pulse power generator can operate in repetitive mode and hence the HPM as well as X-rays may be generated in the repetitive burst. (author)

  2. Hydrogen-Induced Phase Transformation and Microstructure Evolution for Ti-6Al-4V Parts Produced by Electron Beam Melting

    Directory of Open Access Journals (Sweden)

    Natalia Pushilina

    2018-04-01

    Full Text Available In this paper, phase transitions and microstructure evolution in titanium Ti-6Al-4V alloy parts produced by electron beam melting (EBM under hydrogenation was investigated. Hydrogenation was carried out at the temperature of 650 °C to the absolute hydrogen concentrations in the samples of 0.29, 0.58, and 0.90 wt. %. Comparative analysis of microstructure changes in Ti-6Al-4V alloy parts was performed using scanning electron microscopy (SEM, transmission electron microscopy (TEM, and X-ray diffraction (XRD. Furthermore, in-situ XRD was used to investigate the phase transitions in the samples during hydrogenation. The structure of Ti-6Al-4V parts produced by EBM is represented by the α phase plates with the transverse length of 0.2 μm, the β phase both in the form of plates and globular grains, and metastable α″ and ω phases. Hydrogenation to the concentration of 0.29 wt. % leads to the formation of intermetallic Ti3Al phase. The dimensions of intermetallic Ti3Al plates and their volume fraction increase significantly with hydrogen concentration up to 0.58 wt. % along with precipitation of nano-sized crystals of titanium δ hydrides. Individual Ti3Al plates decay into nanocrystals with increasing hydrogen concentration up to 0.9 wt. % accompanied by the increase of proportion and size of hydride plates. Hardness of EBM Ti-6Al-4V alloy decreases with hydrogen content.

  3. Intense pulsed sources of ions and electrons produced by lasers; Sources pulsees intenses d'ions et d'electrons produites par laser

    Energy Technology Data Exchange (ETDEWEB)

    Bourrabier, G [Centre de Recherche de la C.S.F., Corbeville (France); Consoli, T; Slama, L [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

    1966-11-01

    We describe a device for the acceleration of the plasma burst produced by focusing a laser beam into a metal target. We extract the electrons and the ions from the plasma. The maximum current is around 2000 amperes during few microseconds. The study of the effect of the kind of the target on the characteristics of the current shows the great importance of the initial conditions that is the ionisation potential of the target and the energy laser. (authors) [French] On decrit un dispositif destine a accelerer la bouffee de plasma produite par focalisation d'un faisceau laser sur une cible solide. On extrait du plasma les electrons et les ions. Le courant maximum atteint pres de 2000 amperes pendant quelques microsecondes. L'etude de l'effet de la nature de la cible sur les caracteristiques du courant collecte, met en evidence l'importance des conditions initiales (potentiel d'ionisation de la cible, energie du laser). (auteurs)

  4. Time-resolved probing of electron thermal conduction in femtosecond-laser-pulse-produced plasmas

    International Nuclear Information System (INIS)

    Vue, B.T.V.

    1993-06-01

    We present time-resolved measurements of reflectivity, transmissivity and frequency shifts of probe light interacting with the rear of a disk-like plasma produced by irradiation of a transparent solid target with 0.1ps FWHM laser pulses at peak intensity 5 x 10 l4 W/CM 2 . Experimental results show a large increase in reflection, revealing rapid formation of a steep gradient and overdense surface plasma layer during the first picosecond after irradiation. Frequency shifts due to a moving ionization created by thermal conduction into the solid target are recorded. Calculations using a nonlinear thermal heat wave model show good agreement with the measured frequency shifts, further confining the strong thermal transport effect

  5. Zero-point energy effects in anion solvation shells.

    Science.gov (United States)

    Habershon, Scott

    2014-05-21

    By comparing classical and quantum-mechanical (path-integral-based) molecular simulations of solvated halide anions X(-) [X = F, Cl, Br and I], we identify an ion-specific quantum contribution to anion-water hydrogen-bond dynamics; this effect has not been identified in previous simulation studies. For anions such as fluoride, which strongly bind water molecules in the first solvation shell, quantum simulations exhibit hydrogen-bond dynamics nearly 40% faster than the corresponding classical results, whereas those anions which form a weakly bound solvation shell, such as iodide, exhibit a quantum effect of around 10%. This observation can be rationalized by considering the different zero-point energy (ZPE) of the water vibrational modes in the first solvation shell; for strongly binding anions, the ZPE of bound water molecules is larger, giving rise to faster dynamics in quantum simulations. These results are consistent with experimental investigations of anion-bound water vibrational and reorientational motion.

  6. Study of various photomultiplier tubes with muon beams and Cerenkov light produced in electron showers

    International Nuclear Information System (INIS)

    2010-01-01

    The PMTs of the CMS Hadron Forward calorimeter were found to generate a large size signal when their windows were traversed by energetic charged particles. This signal, which is due to Cerenkov light production at the PMT window, could interfere with the calorimeter signal and mislead the measurements. In order to find a viable solution to this problem, the response of four different types of PMTs to muons traversing their windows at different orientations is measured at the H2 beam-line at CERN. Certain kinds of PMTs with thinner windows show significantly lower response to direct muon incidence. For the four anode PMT, a simple and powerful algorithm to identify such events and recover the PMT signal using the signals of the quadrants without window hits is also presented. For the measurement of PMT responses to Cerenkov light, the Hadron Forward calorimeter signal was mimicked by two different setups in electron beams and the PMT performances were compared with each other. Superior performance of particular PMTs was observed.

  7. Kα satellite transitions in elements with 12≤Z≤30 produced by electron incidence

    International Nuclear Information System (INIS)

    Limandri, Silvina P.; Carreras, Alejo C.; Trincavelli, Jorge C.; Bonetto, Rita D.

    2010-01-01

    The emission of x-ray satellite lines in the Kα region of Mg, Si, Sc, Ti, Cr, Fe, Ni, and Zn induced by electron incidence was studied by means of wavelength dispersive spectroscopy. The satellite lines studied were Kα ' , Kα 3 , Kα 4 , Kα 5 , Kα 6 , and two transitions denoted here as Kα 22 and Kα 12 . Energy shifts with respect to the main Kα 1 diagram line and transition probabilities relative to the whole Kα group were determined for a number of lines through a careful spectral processing. The dependence of these parameters, as well as of the Kβ:Kα intensity ratio, on the atomic number was compared with previous experimental and theoretical determinations when available. A discussion about the different mechanisms responsible for vacancy creation involved in the production of double-ionization satellites was performed in the light of the results obtained. Finally, the behavior of the satellite intensities as a function of the incidence energy was discussed for silicon.

  8. Defect structures in YBa/sub 2/Cu/sub 3/O/sub 7-x/ produced by electron irradiation

    International Nuclear Information System (INIS)

    Kirk, M.A.; Baker, M.C.; Liu, J.Z.; Lam, D.J.; Weber, H.W.

    1988-01-01

    Defect structures in YBa/sub 2/Cu/sub 3/O/sub 7-x/ produced by electron irradiation at 300 K were investigated by transmission electron microscopy. Threshold energies for the production of visible defects were determined to be 152 keV and 131 keV (+- 7 keV) in directions near the a and b (b>a) axes (both perpendicular to c, the long axis in the orthorhombic structure), respectively. During above threshold irradiations in an electron flux of 3x10/sup 18/ cm/sup -2/ s/sup -1/, extended defects were observed to form and grow to sizes of 10-50 nm over 1000 s in material thickness 20-200 nm. Such low electron threshold energies suggest oxygen atom displacements with recoil energies near 20 eV. The observation of movement of twin boundaries during irradiation just above threshold suggests movement of the basal plane oxygen atoms by direct displacement or defect migration processes. Crystals irradiated above threshold were observed after about 24 hours to have transformed to a structure heavily faulted on planes perpendicular to the c axis

  9. Improvement of photoneutron spectrum measurement produced by bombardment of 2 GeV electrons above giant dipole resonance region

    International Nuclear Information System (INIS)

    Lee, H. S.; Park, J. S.; Choi, H. D.; Sato, Tatsuhiko; Shin, Kasuo; Ban, Syuichi

    2000-01-01

    Above the Giant Dipole Resonance (GDR) region, high energy photoneutron spectra produced by irradiation of 2.04 GeV electrons into Pb target were measured by Time-of-Flight (TOF) technique. The differential photoneutron yields were obtained at a fixed angle of 90 degrees to the electron beam direction. The TOF system consists of Pilot-U plastic scintillation detector, which has fast response time, and the high speed multiscaler or CAMAC TDC. In the improvement of experimental setup to extend the flight distance to 10.4 m lead to make the measurable energy to 500 MeV from 300 MeV. And using the TDC based electronics lead to use a veto counter. The results were compared with the calculated one by using EGS4 and Modified PICA95. The characteristics of this TOF system was introduced in this paper and the results for several measuring conditions, which are flight distance, TOF electronics, and type of neutron detector, were discussed to improve the accuracy of this measurement

  10. Molecular hydrogen solvated in water – A computational study

    International Nuclear Information System (INIS)

    Śmiechowski, Maciej

    2015-01-01

    The aqueous hydrogen molecule is studied with molecular dynamics simulations at ambient temperature and pressure conditions, using a newly developed flexible and polarizable H 2 molecule model. The design and implementation of this model, compatible with an existing flexible and polarizable force field for water, is presented in detail. The structure of the hydration layer suggests that first-shell water molecules accommodate the H 2 molecule without major structural distortions and two-dimensional, radial-angular distribution functions indicate that as opposed to strictly tangential, the orientation of these water molecules is such that the solute is solvated with one of the free electron pairs of H 2 O. The calculated self-diffusion coefficient of H 2 (aq) agrees very well with experimental results and the time dependence of mean square displacement suggests the presence of caging on a time scale corresponding to hydrogen bond network vibrations in liquid water. Orientational correlation function of H 2 experiences an extremely short-scale decay, making the H 2 –H 2 O interaction potential essentially isotropic by virtue of rotational averaging. The inclusion of explicit polarizability in the model allows for the calculation of Raman spectra that agree very well with available experimental data on H 2 (aq) under differing pressure conditions, including accurate reproduction of the experimentally noted trends with solute pressure or concentration

  11. Soft X-ray generation in gases by means of a pulsed electron beam produced in a high-voltage barier discharge

    NARCIS (Netherlands)

    Azarov, A.V.; Peters, P.J.M.; Boller, Klaus J.

    2007-01-01

    A large area pulsed electron beam is produced by a high-voltage barrier discharge. We compare the properties of the x-rays generated by stopping this beam of electrons in a thin metal foil with those generated by stopping the electrons directly in various gases. The generation of x-rays was

  12. Estimation of abraham solvation equation coefficients for hydrogen bond formation from abraham solvation parameters for solute activity and basicity

    NARCIS (Netherlands)

    Noort, van P.C.M.

    2013-01-01

    Abraham solvation equations find widespread use in environmental chemistry and pharmaco-chemistry. The coefficients in these equations, which are solvent (system) descriptors, are usually determined by fitting experimental data. To simplify the determination of these coefficients in Abraham

  13. Degradation of Dextran Produced by Leuconostoc mesenteroides ATCC 13146 using Electron Beam Radiation

    International Nuclear Information System (INIS)

    Hong, Jun Tack; Yoo, Sun Kyun; Kang, Hyun Suk; Lee, Byung Cheol

    2010-01-01

    Dextrans make up a family of glucans that have contiguous alpha-1.6 glucose linkages. Differences in the different dextrans in volve the types, amount, length, and arrangements of the arrangements of the branch chains. The principle type of branch linkages found are alpha-1.3, but alpha-1.2 and-1.4 branch linkages have been also observed. In recent days. dextrans have been investigated as potential macromolecular carriers for delivery of drugs and proteins, primarily to increase the longeveity of therapeutic agents in the circulation. In most previous researches, linear type of dextrans with molecular weigh of Μ w 10,000 to 100,000 have been applied for development of new type of drug delivery agent. Such a size of dextrans have been manufactured by acid hydrolysis, of which processes are multi-steps and time-consumed. Therefore, this objective of this research is to evaluate the characterization of branched degraded by a electron beam radiation. L. mesenteroides ATCC 13146 was cultured on te agar slant medium with the composition of 3.0 g K 2 HPO 4 , 0.01 g FeSO 4 . H 2 O, 0.01 g MnSO 4 . 7H 2 O, 0.01 g NaCl, 0.05 g CaCl 2 , 0.5g yeast extract, 15 g agar and 30 g sucrose per liter deionized water. Medium pH was adjusted to 6.0 prior to sterilization. Dextran production was conducted in a fermentor a working volume of 5 1 by using 18% sucrose under optimum pH condition. The inoculum was 2% of the working volume. Fermentation conditions are 28 C, 100 rpm agitation, and 1 vvm of aeration. The fermentation process continued until sucrose was consumed completely. The branch degree of dextran was evaluated using dextranase and analyzed by TLC. The air-dry dextran and solution dextran was irradiated at room temperature using a electrostatic accelerator. The irradiation doses ranged between 30 kGy to 80 kGy. After irradiation, processed dextran showed still a large of branched form. The degradation degree was increased as radiation intensity. The average molecular weight

  14. Ion solvation in polymer blends and block copolymer melts: effects of chain length and connectivity on the reorganization of dipoles.

    Science.gov (United States)

    Nakamura, Issei

    2014-05-29

    We studied the thermodynamic properties of ion solvation in polymer blends and block copolymer melts and developed a dipolar self-consistent field theory for polymer mixtures. Our theory accounts for the chain connectivity of polymerized monomers, the compressibility of the liquid mixtures under electrostriction, the permanent and induced dipole moments of monomers, and the resultant dielectric contrast among species. In our coarse-grained model, dipoles are attached to the monomers and allowed to rotate freely in response to electrostatic fields. We demonstrate that a strong electrostatic field near an ion reorganizes dipolar monomers, resulting in nonmonotonic changes in the volume fraction profile and the dielectric function of the polymers with respect to those of simple liquid mixtures. For the parameter sets used, the spatial variations near an ion can be in the range of 1 nm or larger, producing significant differences in the solvation energy among simple liquid mixtures, polymer blends, and block copolymers. The solvation energy of an ion depends substantially on the chain length in block copolymers; thus, our theory predicts the preferential solvation of ions arising from differences in chain length.

  15. Origin of parameter degeneracy and molecular shape relationships in geometric-flow calculations of solvation free energies

    Energy Technology Data Exchange (ETDEWEB)

    Daily, Michael D. [Fundamental and Computational Sciences Directorate, Pacific Northwest National Laboratory, Richland, Washington 99352 (United States); Chun, Jaehun [Energy and Environment Directorate, Pacific Northwest National Laboratory, Richland, Washington 99352 (United States); Heredia-Langner, Alejandro [National Security Directorate, Pacific Northwest National Laboratory, Richland, Washington 99352 (United States); Wei, Guowei [Department of Mathematics, Michigan State University, East Lansing, Michigan 48824 (United States); Baker, Nathan A. [Computational and Statistical Analytics Division, Pacific Northwest National Laboratory, Richland, Washington 99352 (United States)

    2013-11-28

    Implicit solvent models are important tools for calculating solvation free energies for chemical and biophysical studies since they require fewer computational resources but can achieve accuracy comparable to that of explicit-solvent models. In past papers, geometric flow-based solvation models have been established for solvation analysis of small and large compounds. In the present work, the use of realistic experiment-based parameter choices for the geometric flow models is studied. We find that the experimental parameters of solvent internal pressure p = 172 MPa and surface tension γ = 72 mN/m produce solvation free energies within 1 RT of the global minimum root-mean-squared deviation from experimental data over the expanded set. Our results demonstrate that experimental values can be used for geometric flow solvent model parameters, thus eliminating the need for additional parameterization. We also examine the correlations between optimal values of p and γ which are strongly anti-correlated. Geometric analysis of the small molecule test set shows that these results are inter-connected with an approximately linear relationship between area and volume in the range of molecular sizes spanned by the data set. In spite of this considerable degeneracy between the surface tension and pressure terms in the model, both terms are important for the broader applicability of the model.

  16. Electron beam produced in a transient hollow cathode discharge: beam electron distribution function, X-ray emission and solid target ablation

    International Nuclear Information System (INIS)

    Nistor, Magdalena

    2000-01-01

    This research thesis aims at a better knowledge of phenomena occurring during transient hollow cathode discharges. The author first recalls the characteristics of such a discharge which make it different from conventional pseudo-spark discharges. The objective is to characterise the electron beam produced within the discharge, and the phenomena associated with its interaction with a solid or gaseous target, leading to the production of an X ray or visible radiation. Thus, the author reports the measurement (by magnetic deflection) of the whole time-averaged electronic distribution function. Such a knowledge is essential for a better use of the electron beam in applications such as X-ray source or material ablation. As high repetition frequency pulse X ray sources are very interesting tools, he reports the development and characterisation of Bremsstrahlung X rays during a beam-target interaction. He finally addresses the implementation of a spectroscopic diagnosis for the filamentary plasma and the ablation of a solid target by the beam [fr

  17. Water-enhanced solvation of organics

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Jane H. [Univ. of California, Berkeley, CA (United States)

    1993-07-01

    Water-enhanced solvation (WES) was explored for Lewis acid solutes in Lewis base organic solvents, to develop cheap extract regeneration processes. WES for solid solutes was determined from ratios of solubilities of solutes in water-sat. and low-water solvent; both were determined from solid-liquid equilibrium. Vapor-headspace analysis was used to determine solute activity coefficients as function of organic phase water concentration. WES magnitudes of volatile solutes were normalized, set equal to slope of log γs vs xw/xs curve. From graph shape Δ(log γs) represents relative change in solute activity coefficient. Solutes investigated by vapor-headspace analysis were acetic acid, propionic acid, ethanol, 1,2-propylene glycol, 2,3-butylene glycol. Monocarboxylic acids had largest decrease in activity coefficient with water addition followed by glycols and alcohols. Propionic acid in cyclohexanone showed greatest water-enhancement Δ(log γacid)/Δ(xw/xacid) = -0.25. In methylcyclohexanone, the decrease of the activity coefficient of propionic acid was -0.19. Activity coefficient of propionic acid in methylcyclohexanone stopped decreasing once the water reached a 2:1 water to acid mole ratio, implying a stoichiometric relation between water, ketone, and acid. Except for 2,3-butanediol, activity coefficients of the solutes studied decreased monotonically with water content. Activity coefficient curves of ethanol, 1,2-propanediol and 2,3-butanediol did not level off at large water/solute mole ratio. Solutes investigated by solid-liquid equilibrium were citric acid, gallic acid, phenol, xylenols, 2-naphthol. Saturation concentration of citric acid in anhydrous butyl acetate increased from 0.0009 to 0.087 mol/L after 1.3 % (g/g) water co-dissolved into organic phase. Effect of water-enhanced solvation for citric acid is very large but very small for phenol and its derivatives.

  18. New chiral zwitterionic phosphorus heterocycles: synthesis, structure, properties and application as chiral solvating agents.

    Science.gov (United States)

    Sheshenev, Andrey E; Boltukhina, Ekaterina V; Grishina, Anastasiya A; Cisařova, Ivana; Lyapkalo, Ilya M; Hii, King Kuok Mimi

    2013-06-17

    A family of new chiral zwitterionic phosphorus-containing heterocycles (zPHC) have been derived from methylene-bridged bis(imidazolines). These structures were unambiguously determined, including single-crystal XRD analysis for two compounds. The stability, acid/base and electronic properties of these dipolar phosphorus heterocycles were subsequently investigated. zPHCs can be successfully employed as a new class of chiral solvating agents for the enantiodifferentiation of chiral carboxylic and sulfonic acids by NMR spectroscopy. The stoichiometry and binding constants for the donor-acceptor complexes formed were established by NMR titration methods. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Free terminal amines in DNA-binding peptides alter the product distribution from guanine radicals produced by single electron oxidation.

    Science.gov (United States)

    Konigsfeld, Katie M; Lee, Melissa; Urata, Sarah M; Aguilera, Joe A; Milligan, Jamie R

    2012-03-01

    Electron deficient guanine radical species are major intermediates produced in DNA by the direct effect of ionizing irradiation. There is evidence that they react with amine groups in closely bound ligands to form covalent crosslinks. Crosslink formation is very poorly characterized in terms of quantitative rate and yield data. We sought to address this issue by using oligo-arginine ligands to model the close association of DNA and its binding proteins in chromatin. Guanine radicals were prepared in plasmid DNA by single electron oxidation. The product distribution derived from them was assayed by strand break formation after four different post-irradiation incubations. We compared the yields of DNA damage produced in the presence of four ligands in which neither, one, or both of the amino and carboxylate termini were blocked with amides. Free carboxylate groups were unreactive. Significantly higher yields of heat labile sites were observed when the amino terminus was unblocked. The rate of the reaction was characterized by diluting the unblocked amino group with its amide blocked derivative. These observations provide a means to develop quantitative estimates for the yields in which these labile sites are formed in chromatin by exposure to ionizing irradiation.

  20. Cross sections of electron excitation out of metastable helium levels with a fast metastable target product produced via charge exchange

    International Nuclear Information System (INIS)

    Lagus, M.E.; Boffard, J.B.; Anderson, L.W.; Lin, C.C.

    1996-01-01

    Absolute direct cross sections for electron excitation out of the 2 3 S level and into the 3 3 D, 4 3 D, and 3 3 S levels of the helium atom from threshold to 500 eV and into the 3 3 P level over a more limited energy range have been measured using a fast metastable atomic beam target. We produce the metastable atoms via near-resonant charge exchange between a 1.6-keV He + ion beam and Cs vapor. Because this reaction is highly nonresonant with the ground state of helium, the charge-transfer process yields a primarily metastable beam. We use a thermal detector which we calibrate with ions to measure absolutely the neutral beam flux. The atomic beam is crossed by an electron beam, and we collect the resulting fluorescence at right angles to both the electron and atomic beams. We obtain the cross sections for excitation out of the 2 3 S level into the various excited levels by monitoring the emission out of the excited level of interest. copyright 1996 The American Physical Society

  1. The solvation reaction field for a hydrogen atom in a dielectric continuum

    International Nuclear Information System (INIS)

    Chipman, D.M.

    1996-01-01

    A reaction field exists even for a nonpolar solute embedded in a spherical cavity within a surrounding homogeneous dielectric continuum. This arises from the tail of the electronic wave function that penetrates beyond the cavity boundary into the dielectric region. This effect, which is neglected or treated only in cursory fashion in most reaction field implementations, is examined in detail for the simple case of a ground state hydrogen atom, where very accurate solutions of the relevant equations can be obtained. Properties considered include the penetration of the electron outside the cavity, the electronic density at the nucleus, the electron binding energy, the electrostatic free energy of solvation, the polarizability, and the vertical 1s→2p excitation energy. Also, the effect of the common approximation of neglecting the volume polarization and treating only the surface polarization contribution to the reaction field is critically evaluated. copyright 1996 American Institute of Physics

  2. Transport of secondary electrons and reactive species in ion tracks

    Science.gov (United States)

    Surdutovich, Eugene; Solov'yov, Andrey V.

    2015-08-01

    The transport of reactive species brought about by ions traversing tissue-like medium is analysed analytically. Secondary electrons ejected by ions are capable of ionizing other molecules; the transport of these generations of electrons is studied using the random walk approximation until these electrons remain ballistic. Then, the distribution of solvated electrons produced as a result of interaction of low-energy electrons with water molecules is obtained. The radial distribution of energy loss by ions and secondary electrons to the medium yields the initial radial dose distribution, which can be used as initial conditions for the predicted shock waves. The formation, diffusion, and chemical evolution of hydroxyl radicals in liquid water are studied as well. COST Action Nano-IBCT: Nano-scale Processes Behind Ion-Beam Cancer Therapy.

  3. Protonic and Electronic Charge Carriers in Solvated Biomacromolecules

    Science.gov (United States)

    1989-01-01

    was less than 1% of that expected from Couloub’s law]. When dryer samples (less than 5% water ), were electrolysed , the amount of oxygen could only be...2. The methodology involved the adsorption of water and other organic liquids on biomacromolecules and subsequent solid-state electrolysis. 3. The...in contrast, was not found in an electrolysis product even when water was the adsorbate., 6. -The conclusion is that protonic conductance in

  4. Characteristic and non-characteristic X-ray yields produced from thick Ti element by sub-relativistic electrons

    International Nuclear Information System (INIS)

    Yadav, Namita; Kumar, Sunil; Bhatt, Pragya; Singh, Raj; Singh, B.K.; Shanker, R.

    2012-01-01

    Highlights: ► The X-ray spectra of a thick Ti element by 10–25 keV electron impact are obtained. ► Measured Ti K α yields are found to be in good agreement with PWBA theory. ► Doubly differential bremsstrahlung yields agree reasonably with MC simulation. ► Average value of the ratio K α /(K α + K β ) of Ti is found to be 0.881 ± 0.003. -- Abstract: Measurements are performed to study the electron impact energy dependence of doubly differential bremsstrahlung yields (DDBY) and of characteristic Ti K α line yields produced from sub-relativistic electrons (10–25 keV) colliding with a thick Ti (Z = 22) target. The emitted radiation is detected by a Si-PIN photo-diode detector with energy resolution (FWHM) of 180 eV at 5.9 keV. The measured data of DDBY are compared with the results predicted by Monte-Carlo (MC) simulations using the general purpose PENELOPE code. A reasonable agreement is found between experimental and simulation results within the experimental uncertainty of measurements of 12%. Characteristic Ti K α yields are obtained for the considered impact energy range and they are compared with the existing theoretical results. A good agreement is found between the present measurements and the theoretical calculations. Furthermore, data are presented for impact energy dependence of the ratio K α /(K α + K β ) of a thick Ti target under impact of 10–25 keV electrons. The ratio shows a very weak dependence on impact energy in the studied range. The average value of the ratio is found to be 0.881 ± 0.003.

  5. High-power, high-brightness pseudospark-produced electron beam driven by improved pulse line accelerator

    International Nuclear Information System (INIS)

    Junbino Zhu; Mingchang Wang; Zhijiang Wang

    1995-01-01

    A high power (200KV), intense current density, low emittance (71mmmrad), high brightness (8x10 10 A/m rad) electron beam was generated in the 10cm long, high-voltage-resistive multi-gap hollow cathode pseudospark chamber filled with 15pa nitrogen and driven by an improved pulse line accelerator. The beam was ejected with the 1mm diameter, the 2.2KA beam current, and the 400ns pulse length, and could propagated 20cm in the drift tube. At a distance of 5cm from the anode it penetrated consecutively an acid-sensitive discoloring film and a 0.05mm-thick copper foil both stuck closely, left 0.6mm and 0.3mm holes on them, respectively. That 10 shots on an acid-sensitive film produced a hole of 1.6mm at 7cm downstream of anode showed its good repeatability. After 60 shots the pseudospark discharge chamber was disassembled and observed that almost no destructive damage traces left on the surfaces of its various electrodes and insulators. But on almost all the surfaces of changeable central hole parts installed on intermediate electrodes there are traces of electron emission from the sides facing the anode and of bombardment on the sides facing the cathode, in contrast with which on the front- and back-surfaces of hollow cathode no visible traces of electron emission from then was observed. In addition, there were different tints, strip-like regions on the side of anode facing the cathode. Another interesting phenomenon was that there were a set of concentric circular or elliptical ring pattern on the acid-sensitive discoloring film got at 5cm from the anode and observed tinder a metallograph. It seems that the pseudospark electron beam is Laminar beam i.e, being possessed of a multi-layer structure, at least in the case of multi-gap pseudospark discharge chamber. It was found experimentally that the quality of pseudospark electron beam is much better than that of the cold-cathode electron beam

  6. Cluster expansion of the solvation free energy difference: Systematic improvements in the solvation of single ions

    Science.gov (United States)

    Pliego, Josefredo R.

    2017-07-01

    The cluster expansion method has been used in the imperfect gas theory for several decades. This paper proposes a cluster expansion of the solvation free energy difference. This difference, which results from a change in the solute-solvent potential energy, can be written as the logarithm of a finite series. Similar to the Mayer function, the terms in the series are related to configurational integrals, which makes the integrand relevant only for configurations of the solvent molecules close to the solute. In addition, the terms involve interaction of solute with one, two, and so on solvent molecules. The approach could be used for hybrid quantum mechanical and molecular mechanics methods or mixed cluster-continuum approximation. A simple form of the theory was applied for prediction of pKa in methanol; the results indicated that three explicit methanol molecules and the dielectric continuum lead to a root of mean squared error (RMSE) of only 1.3 pKa units, whereas the pure continuum solvation model based on density method leads to a RMSE of 6.6 pKa units.

  7. Ab initio studies on the solvation, electronic structures and intracluster reactions in M(+)L(n), with M(+)=magnesium and calcium singly-charged ions, L=water, methanol, ammonia, and n=1-6, and the elimination of a hydrogen atom in H atom in hydrated sodium clusters

    Science.gov (United States)

    Chan, Ka Wai

    The solvation and electronic structures of M+Ln, with M+ = Mg+ and Cat, L = H2O, CH 3OH and NH3, n=1-6 were investigated by ab initio calculations using G03 package and density functional theory based ab initio molecular dynamics (AIMD) simulations with projector augmented-wave (PAW) method and a planewave basis set using Vienna Ab initio Simulation Package (VASP). Furthermore, ab initio studies on the intracluster reactions of Mg+ and Ca+ ions with different solvent molecules, H2O, CH3OH and NH3, were also done using G03 package. Finally, the elimination of a H atom in Na(H2O)n was studied. Such studies on the interactions and reactivity in gas clusters can provide insights into their analogies existing in condense phase. Interactions of Mg+ and Ca+ ions in different solvent molecules, H2O, CH3OH and NH3, were calculated with B3LYP and MP2 methods with basis sets 6-31+g** and 6-311+g**. A systematic comparison on the structures and reactivities of these clusters should provide a better understanding on the interplay of the ion-solvent, solvent-solvent, and electron-solvent interactions. It can provide a better understanding on the structures and bonding of complexes having analogies to those existing in condense phase. For Mg+(CH3OH)n and Ca+(CH 3OH)n, both H-elimination from OH/CH bond and CH3-elimination were investigated. H-elimination from O---H bond becomes more accessible for large cluster due to the diffusion of electron density to O---H bond. Studies on the H-elimination in Mg+(NH3)n and H-elimination from C---H bond in Mg+(CH3OH) n show that the reaction barriers flatten above 20 kcal/mol as n reaches 4 and above. These calculation results prove that the source of loss of H atom in ground state Mg+(CH3OH)n should be through the O---H bond rather than through the C---H bond. Compared to Mg+(CH3OH)n, the reaction barriers for H-elimination in Mg+(NH3)n is much larger, which is in consistent with the experimental observation of little H-elimination for Mg

  8. Order and correlation contributions to the entropy of hydrophobic solvation

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Maoyuan; Besford, Quinn Alexander; Mulvaney, Thomas; Gray-Weale, Angus, E-mail: gusgw@gusgw.net [School of Chemistry, The University of Melbourne, Victoria 3010 (Australia)

    2015-03-21

    The entropy of hydrophobic solvation has been explained as the result of ordered solvation structures, of hydrogen bonds, of the small size of the water molecule, of dispersion forces, and of solvent density fluctuations. We report a new approach to the calculation of the entropy of hydrophobic solvation, along with tests of and comparisons to several other methods. The methods are assessed in the light of the available thermodynamic and spectroscopic information on the effects of temperature on hydrophobic solvation. Five model hydrophobes in SPC/E water give benchmark solvation entropies via Widom’s test-particle insertion method, and other methods and models are tested against these particle-insertion results. Entropies associated with distributions of tetrahedral order, of electric field, and of solvent dipole orientations are examined. We find these contributions are small compared to the benchmark particle-insertion entropy. Competitive with or better than other theories in accuracy, but with no free parameters, is the new estimate of the entropy contributed by correlations between dipole moments. Dipole correlations account for most of the hydrophobic solvation entropy for all models studied and capture the distinctive temperature dependence seen in thermodynamic and spectroscopic experiments. Entropies based on pair and many-body correlations in number density approach the correct magnitudes but fail to describe temperature and size dependences, respectively. Hydrogen-bond definitions and free energies that best reproduce entropies from simulations are reported, but it is difficult to choose one hydrogen bond model that fits a variety of experiments. The use of information theory, scaled-particle theory, and related methods is discussed briefly. Our results provide a test of the Frank-Evans hypothesis that the negative solvation entropy is due to structured water near the solute, complement the spectroscopic detection of that solvation structure by

  9. Solvation structures of lithium halides in methanol–water mixtures

    International Nuclear Information System (INIS)

    Sarkar, Atanu; Dixit, Mayank Kumar; Tembe, B.L.

    2015-01-01

    Highlights: • Potentials of mean force for Li + -halides are calculated in methanol–water mixtures. • Stable CIP for x methanol = 1.0 becomes unstable at and below x methanol = 0.75. • The Li + ion is preferentially solvated by methanol molecules. • The halide ions are preferentially solvated by water molecules. - Abstract: The potentials of mean force (PMFs) for the ion pairs, Li + −Cl − , Li + −Br − and Li + −I − have been calculated in five methanol–water compositions. The results obtained are verified by trailing the trajectories and calculating the ion pair distance residence times. Local structures around the ions are studied using the radial distribution functions, density profiles, orientational correlation functions, running coordination numbers and excess coordination numbers. The major change in PMF is observed as the methanol mole fraction (x methanol ) is changed from 1.0 to 0.75. The stable contact ion pair occurring for x methanol = 1.0 becomes unstable at and below x methanol = 0.75. The preferential solvation data show that the halide ions are always preferentially solvated by water molecules. Although the lithium ion is preferentially solvated by methanol molecules, there is significant affinity towards water molecules as well

  10. Ultra High Intensity laser produced fast electron transport in under-dense and over-dense matter

    International Nuclear Information System (INIS)

    Manclossi, Mauro

    2006-01-01

    This thesis is related to inertial fusion research, and particularly concerns the approach to fast ignition, which is based on the use of ultra-intense laser pulses to ignite the thermonuclear fuel. Until now, the feasibility of this scheme has not been proven and depends on many fundamental aspects of the underlying physics, which are not yet fully understood and which are also very far from controls. The main purpose of this thesis is the experimental study of transport processes in the material over-dense (solid) and under-dense (gas jet) of a beam of fast electrons produced by pulse laser at a intensity of some 10 19 Wcm -2 . (author)

  11. Photo-electron spectroscopy using synchrotron radiation of molecular radicals and fragments produced by laser photo-dissociation

    International Nuclear Information System (INIS)

    Nahon, Laurent

    1991-01-01

    This research thesis reports the combined use of a laser and of a synchrotron radiation in order to respectively photo-dissociate a molecule and to photo-ionize fragments which are analysed by photo-electron spectroscopy. This association allows, on the one hand, radical photo-ionization to be studied, and, on the other hand, polyatomic molecule photo-dissociation to be studied. The author studied the photo-excitation and/or photo-ionization in layer 4d (resp. 3d) of atomic iodine (resp. bromine) produced almost complete laser photo-dissociation of I_2 (resp. Br_2). He discuses the processes of relaxation of transitions from valence 4d to 5p (resp. 3d to 4p) which occur either by direct self-ionization or by resonant Auger effect, and reports the study of photo-dissociation of s-tetrazine (C_2N_4H_2) [fr

  12. Contribution to the theoretical study of a high power microwave radiation produced by a relativistic electron beam

    International Nuclear Information System (INIS)

    Sellem, F.

    1997-01-01

    This thesis is dedicated to the study of microwave radiation produced by relativistic electron beams. The vircator (virtual cathode oscillator) is a powerful microwave source based on this principle. This device is described but the complexity of the physical processes involved makes computer simulation necessary before proposing a simplified model. The existent M2V code has been useful to simulate the behaviour of a vircator but the representation of some phenomena such as hot points, the interaction of waves with particles lacks reliability. A new code CODEX has been written, it can solve Maxwell equations on a double mesh system by a finite difference method. The electric and magnetic fields are directly computed from the scalar and vectorial potentials. This new code has been satisfactorily tested on 3 configurations: the bursting of an electron beam in vacuum, the evolution of electromagnetic fields in diode and the propagation of waves in a wave tube. CODEX has been able to simulate the behaviour of a vircator, the frequency and power are well predicted and some contributions to the problem of origin of microwave production have been made. It seems that the virtual cathode is not directly involved in the microwave production. (A.C.)

  13. Electron transfer from H2 and Ar to stored multiply charged argon ions produced by synchrotron radiation

    International Nuclear Information System (INIS)

    Kravis, S.D.; Church, D.A.; Johnson, B.M.; Meron, M.; Jones, K.W.; Levin, J.C.; Sellin, I.A.; Azuma, Y.; Berrah-Mansour, N.; Berry, H.G.; Druetta, M.

    1992-01-01

    The rate coefficients for electron transfer from Ar and H 2 to Ar q+ ions (3≤q≤6) have been measured using an ion-storage technique in a Penning ion trap. The ions were produced in the trap by K-shell photoionization of Ar atoms, using broadband synchrotron x-ray radiation. K-electron removal resulted in vacancy cascading, yielding a distribution of argon-ion charge states peaked near Ar 4+ . The stored ion gas had an initial temperature near 480 K. The basic data determining the rate coefficients k(Ar q+ ) are the storage time constants of each charge state in the trap, in the presence of a measured pressure of target gas. The results of the measurements (in units of 10 -9 cm 3 s -1 ) are k(Ar 3+ ,H 2 )=4.3(0.7), k(Ar 3+ ,Ar)=1.6(0.2), k(Ar 4+ ,H 2 )=5.2(0.6), k(Ar 4+ ,Ar)=2.5(0.3), k(Ar 5+ ,H 2 )=5.9(0.7), k(Ar 5+ ,Ar)=2.9(0.3), k(Ar 6+ ,H 2 )=8.5(1.2), and k(Ar 6+ ,Ar)=2.5(0.3)

  14. Characterization of an Additive Manufactured TiAl Alloy-Steel Joint Produced by Electron Beam Welding.

    Science.gov (United States)

    Basile, Gloria; Baudana, Giorgio; Marchese, Giulio; Lorusso, Massimo; Lombardi, Mariangela; Ugues, Daniele; Fino, Paolo; Biamino, Sara

    2018-01-17

    In this work, the characterization of the assembly of a steel shaft into a γ-TiAl part for turbocharger application, obtained using Electron Beam Welding (EBW) technology with a Ni-based filler, was carried out. The Ti-48Al-2Nb-0.7Cr-0.3Si (at %) alloy part was produced by Electron Beam Melting (EBM). This additive manufacturing technology allows the production of a lightweight part with complex shapes. The replacement of Nickel-based superalloys with TiAl alloys in turbocharger automotive applications will lead to an improvement of the engine performance and a substantial reduction in fuel consumption and emission. The welding process allows a promising joint to be obtained, not affecting the TiAl microstructure. Nevertheless, it causes the formation of diffusive layers between the Ni-based filler and both steel and TiAl, with the latter side being characterized by a very complex microstructure, which was fully characterized in this paper by means of Scanning Electron Microscopy, Energy Dispersive X-ray Spectroscopy, and nanoindentation. The diffusive interface has a thickness of about 6 µm, and it is composed of several layers. Specifically, from the TiAl alloy side, we find a layer of Ti₃Al followed by Al₃NiTi₂ and AlNi₂Ti. Subsequently Ni becomes more predominant, with a first layer characterized by abundant carbide/boride precipitation, and a second layer characterized by Si-enrichment. Then, the chemical composition of the Ni-based filler is gradually reached.

  15. Characterization of an Additive Manufactured TiAl Alloy—Steel Joint Produced by Electron Beam Welding

    Directory of Open Access Journals (Sweden)

    Gloria Basile

    2018-01-01

    Full Text Available In this work, the characterization of the assembly of a steel shaft into a γ-TiAl part for turbocharger application, obtained using Electron Beam Welding (EBW technology with a Ni-based filler, was carried out. The Ti-48Al-2Nb-0.7Cr-0.3Si (at % alloy part was produced by Electron Beam Melting (EBM. This additive manufacturing technology allows the production of a lightweight part with complex shapes. The replacement of Nickel-based superalloys with TiAl alloys in turbocharger automotive applications will lead to an improvement of the engine performance and a substantial reduction in fuel consumption and emission. The welding process allows a promising joint to be obtained, not affecting the TiAl microstructure. Nevertheless, it causes the formation of diffusive layers between the Ni-based filler and both steel and TiAl, with the latter side being characterized by a very complex microstructure, which was fully characterized in this paper by means of Scanning Electron Microscopy, Energy Dispersive X-ray Spectroscopy, and nanoindentation. The diffusive interface has a thickness of about 6 µm, and it is composed of several layers. Specifically, from the TiAl alloy side, we find a layer of Ti3Al followed by Al3NiTi2 and AlNi2Ti. Subsequently Ni becomes more predominant, with a first layer characterized by abundant carbide/boride precipitation, and a second layer characterized by Si-enrichment. Then, the chemical composition of the Ni-based filler is gradually reached.

  16. A New Inversion Routine to Produce Vertical Electron-Density Profiles from Ionospheric Topside-Sounder Data

    Science.gov (United States)

    Wang, Yongli; Benson, Robert F.

    2011-01-01

    Two software applications have been produced specifically for the analysis of some million digital topside ionograms produced by a recent analog-to-digital conversion effort of selected analog telemetry tapes from the Alouette-2, ISIS-1 and ISIS-2 satellites. One, TOPIST (TOPside Ionogram Scalar with True-height algorithm) from the University of Massachusetts Lowell, is designed for the automatic identification of the topside-ionogram ionospheric-reflection traces and their inversion into vertical electron-density profiles Ne(h). TOPIST also has the capability of manual intervention. The other application, from the Goddard Space Flight Center based on the FORTRAN code of John E. Jackson from the 1960s, is designed as an IDL-based interactive program for the scaling of selected digital topside-sounder ionograms. The Jackson code has also been modified, with some effort, so as to run on modern computers. This modification was motivated by the need to scale selected ionograms from the millions of Alouette/ISIS topside-sounder ionograms that only exist on 35-mm film. During this modification, it became evident that it would be more efficient to design a new code, based on the capabilities of present-day computers, than to continue to modify the old code. Such a new code has been produced and here we will describe its capabilities and compare Ne(h) profiles produced from it with those produced by the Jackson code. The concept of the new code is to assume an initial Ne(h) and derive a final Ne(h) through an iteration process that makes the resulting apparent-height profile fir the scaled values within a certain error range. The new code can be used on the X-, O-, and Z-mode traces. It does not assume any predefined profile shape between two contiguous points, like the exponential rule used in Jackson s program. Instead, Monotone Piecewise Cubic Interpolation is applied in the global profile to keep the monotone nature of the profile, which also ensures better smoothness

  17. Difference rule-a new thermodynamic principle: prediction of standard thermodynamic data for inorganic solvates.

    Science.gov (United States)

    Jenkins, H Donald Brooke; Glasser, Leslie

    2004-12-08

    We present a quite general thermodynamic "difference" rule, derived from thermochemical first principles, quantifying the difference between the standard thermodynamic properties, P, of a solid n-solvate (or n-hydrate), n-S, containing n molecules of solvate, S (water or other) and the corresponding solid parent (unsolvated) salt: [P[n-solvate] - P[parent

  18. Structural aspects of the solvation shell of lysine and acetylated lysine: A Car-Parrinello and classical molecular dynamics investigation

    International Nuclear Information System (INIS)

    Carnevale, V.; Raugei, S.

    2009-01-01

    Lysine acetylation is a post-translational modification, which modulates the affinity of protein-protein and/or protein-DNA complexes. Its crucial role as a switch in signaling pathways highlights the relevance of charged chemical groups in determining the interactions between water and biomolecules. A great effort has been recently devoted to assess the reliability of classical molecular dynamics simulations in describing the solvation properties of charged moieties. In the spirit of these investigations, we performed classical and Car-Parrinello molecular dynamics simulations on lysine and acetylated-lysine in aqueous solution. A comparative analysis between the two computational schemes is presented with a focus on the first solvation shell of the charged groups. An accurate structural analysis unveils subtle, yet statistically significant, differences which are discussed in connection to the significant electronic density charge transfer occurring between the solute and the surrounding water molecules.

  19. Water Evaporation and Conformational Changes from Partially Solvated Ubiquitin

    Directory of Open Access Journals (Sweden)

    Saravana Prakash Thirumuruganandham

    2010-01-01

    Full Text Available Using molecular dynamics simulation, we study the evaporation of water molecules off partially solvated ubiquitin. The evaporation and cooling rates are determined for a molecule at the initial temperature of 300 K. The cooling rate is found to be around 3 K/ns, and decreases with water temperature in the course of the evaporation. The conformation changes are monitored by studying a variety of intermediate partially solvated ubiquitin structures. We find that ubiquitin shrinks with decreasing hydration shell and exposes more of its hydrophilic surface area to the surrounding.

  20. Dipole moments of molecules solvated in helium nanodroplets

    International Nuclear Information System (INIS)

    Stiles, Paul L.; Nauta, Klaas; Miller, Roger E.

    2003-01-01

    Stark spectra are reported for hydrogen cyanide and cyanoacetylene solvated in helium nanodroplets. The goal of this study is to understand the influence of the helium solvent on measurements of the permanent electric dipole moment of a molecule. We find that the dipole moments of the helium solvated molecules, calculated assuming the electric field is the same as in vacuum, are slightly smaller than the well-known gas-phase dipole moments of HCN and HCCCN. A simple elliptical cavity model quantitatively accounts for this difference, which arises from the dipole-induced polarization of the helium

  1. Differential geometry based solvation model II: Lagrangian formulation.

    Science.gov (United States)

    Chen, Zhan; Baker, Nathan A; Wei, G W

    2011-12-01

    Solvation is an elementary process in nature and is of paramount importance to more sophisticated chemical, biological and biomolecular processes. The understanding of solvation is an essential prerequisite for the quantitative description and analysis of biomolecular systems. This work presents a Lagrangian formulation of our differential geometry based solvation models. The Lagrangian representation of biomolecular surfaces has a few utilities/advantages. First, it provides an essential basis for biomolecular visualization, surface electrostatic potential map and visual perception of biomolecules. Additionally, it is consistent with the conventional setting of implicit solvent theories and thus, many existing theoretical algorithms and computational software packages can be directly employed. Finally, the Lagrangian representation does not need to resort to artificially enlarged van der Waals radii as often required by the Eulerian representation in solvation analysis. The main goal of the present work is to analyze the connection, similarity and difference between the Eulerian and Lagrangian formalisms of the solvation model. Such analysis is important to the understanding of the differential geometry based solvation model. The present model extends the scaled particle theory of nonpolar solvation model with a solvent-solute interaction potential. The nonpolar solvation model is completed with a Poisson-Boltzmann (PB) theory based polar solvation model. The differential geometry theory of surfaces is employed to provide a natural description of solvent-solute interfaces. The optimization of the total free energy functional, which encompasses the polar and nonpolar contributions, leads to coupled potential driven geometric flow and PB equations. Due to the development of singularities and nonsmooth manifolds in the Lagrangian representation, the resulting potential-driven geometric flow equation is embedded into the Eulerian representation for the purpose of

  2. Forward directed x-ray from source produced by relativistic electrons from a Self-Modulated Laser Wakefield Accelerator

    Science.gov (United States)

    Lemos, Nuno; Albert, Felicie; Shaw, Jessica; King, Paul; Milder, Avi; Marsh, Ken; Pak, Arthur; Joshi, Chan

    2017-10-01

    Plasma-based particle accelerators are now able to provide the scientific community with novel light sources. Their applications span many disciplines, including high-energy density sciences, where they can be used as probes to explore the physics of dense plasmas and warm dense matter. A recent advance is in the experimental and theoretical characterization of x-ray emission from electrons in the self-modulated laser wakefield regime (SMLWFA) where little is known about the x-ray properties. A series of experiments at the LLNL Jupiter Laser Facility, using the 1 ps 150 J Titan laser, have demonstrated low divergence electron beams with energies up to 300 MeV and 6 nCs of charge, and betatron x-rays with critical energies up to 20 keV. This work identifies two other mechanisms which produce high energy broadband x-rays and gamma-rays from the SMLWFA: Bremsstrahlung and inverse Compton scattering. We demonstrate the use of Compton scattering and bremsstrahlung to generate x/Gamma-rays from 3 keV up to 1.5 MeV with a source size of 50um and a divergence of 100 mrad. This work is an important step towards developing this x-ray light source on large-scale international laser facilities, and also opens up the prospect of using them for applications. This work was performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under the contract DE-AC52-07NA27344. Lawrence Livermore National Security, LLC.

  3. Development and application of QM/MM methods to study the solvation effects and surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Dibya, Pooja Arora [Iowa State Univ., Ames, IA (United States)

    2010-01-01

    . Chapter 2 illustrates the methodology of the interface of the EFP method with the configuration interaction with single excitations (CIS) method to study solvent effects in excited states. Chapter 3 discusses the study of the adiabatic electron affinity of the hydroxyl radical in aqueous solution and in micro-solvated clusters using a QM/EFP method. Chapter 4 describes the study of etching and diffusion of oxygen atom on a reconstructed Si(100)-2 x 1 surface using a hybrid QM/MM embedded cluster model (SIMOMM). Chapter 4 elucidates the application of the EFP method towards the understanding of the aqueous ionization potential of Na atom. Finally, a general conclusion of this dissertation work and prospective future direction are presented in Chapter 6.

  4. A study of the luminosity produced by an electron beam-emitting rocket in the polar ionosphere: ECHO 7

    International Nuclear Information System (INIS)

    Franz, R.C.

    1991-01-01

    Optical observations made during the ECHO 7 experiment show for the first time the luminous manifestations of the Beam-Plasma-Interaction in a space environment. The optical observations were made using photometers and a low-light-level television camera over an altitude range of 90 to 290 km. Imagery, obtained for the first time in the ECHO series, show the luminous spatial characteristics of the BPI including the formation of diffuse luminous columns extending along the magnetic field in the same and opposite directions as beam propagation. The beam-plasma-discharge (BPD) evolved from the BPI, igniting first about 140 km, and quenching at 115 km. The BPD appeared as discrete enhancements in the intensity of portions of the diffuse columns extending 200 to 225 m along the magnetic field line. Relaxations oscillations, or non-steady BPD with frequencies between 20 and 45 Hz were observed prior to BPD initiation. At 108 km, the distinct Larmor spiral structure of the beam became visible for distance of about 300 meters along the field. Periodic attitude control system (ACS) Nitrogen gas releases producing spectacular luminosity patterns were seen during the gun operation throughout the flight. The injected gas affected the vehicle neutralization current flow pattern causing current to be concentrated in the gas plume as it flowed toward the MAIN payload. In the absence of ACS gas, the luminosity pattern surrounding the MAIN payload showed an asymmetry, being brighter at the opposite end of the MAIN away from the electron gun

  5. Measurements of Electron Density Profiles of Plasmas Produced by Nike KrF Laser for Laser Plasma Instability (LPI) Research

    Science.gov (United States)

    Oh, Jaechul; Weaver, J. L.; Obenschain, S. P.; Schmitt, A. J.; Kehne, D. M.; Karasik, M.; Chan, L.-Y.; Serlin, V.; Phillips, L.

    2013-10-01

    Knowing spatial profiles of electron density (ne) in the underdense coronal region (n Nike LPI experiment, a side-on grid imaging refractometer (GIR) was deployed for measuring the underdense plasma profiles. Plasmas were produced from flat CH targets illuminated by Nike KrF laser with total energies up to 1 kJ of 0.5 ~ 1 nsec FWHM pulses. The GIR resolved ne up to 3 ×1021 /cm3 in space taking 2D snapshot images of probe laser (λ = 263 nm, Δt = 10 ps) beamlets (50 μm spacing) refracted by the plasma at a selected time during the laser illumination. The individual beamlet transmittances were also measured for Te estimation. Time-resolved spectrometers with an absolute-intensity-calibrated photodiode array and a streak camera simultaneously detected light emission from the plasma in spectral ranges relevant to Raman (SRS) and two plasmon decay instabilities. The measured spatial profiles are compared with simulation results from the FAST3D radiation hydrocode and their effects on the LPI observations are investigated. Work supported by DoE/NNSA and performed at Naval Research Laboratory.

  6. Thermodynamics of solvation and solvophobic effect in formamide

    International Nuclear Information System (INIS)

    Sedov, I.A.; Stolov, M.A.; Solomonov, B.N.

    2013-01-01

    Highlights: • Enthalpies of solution of apolar organic compounds in formamide were measured. • Gibbs free energies of solution were experimentally determined. • Influence of the solvophobic effect on solvation thermodynamics was studied. • Thermodynamic features of solutions in formamide resemble those of aqueous solutions. -- Abstract: Using semi-adiabatic calorimetry, we measured the enthalpies of solution for various low-polar compounds including alkanes, aromatic hydrocarbons and their halogenated derivatives in formamide at temperature of 298 K. For the same compounds, the values of limiting activity coefficients in formamide were determined using GC headspace analysis at 298 K, and Gibbs free energies of solution and solvation were calculated. Based on these data and the available literature values of the Gibbs free energy of solvation in formamide for a number of other low-polar solutes, a study of the solvophobic effect in this solvent is performed, and its resemblance to the hydrophobic effect in aqueous solutions is demonstrated. It is shown that the contribution of the solvophobic effect into the solvation Gibbs free energy in formamide is much higher than that in aliphatic alcohols, but lower than that in water. Like in water, the magnitude of this contribution for different solutes linearly increases with the solute molecular volume. Solvophobic effect also significantly affects the enthalpies of dissolution in formamide, causing them to be more negative in the case of alkanes and more positive in the case of arenes

  7. Isotope effect in enthalpy of solvation of the lithium ion

    International Nuclear Information System (INIS)

    Krestov, G.A.; Egorov, G.I.; Korolev, V.P.

    1989-01-01

    At 298.15 K, the authors determined the standard enthalpies of solution for 6 LiCl and 7 LiCl in water, heavy water, dimethylsulfoxide (DMSO) and aqueous solutions of DMSO. The authors have established that solvation of 6 Li + is differentiated in water and DMSO to a greater degree than for 7 Li +

  8. The solvation of carbohydrates in dimethylsulfoxide and water

    International Nuclear Information System (INIS)

    Berger, S.; Diaz, M.D.; Horwat, Ch.

    1999-01-01

    The solvation of sucrose and other carbohydrates in DMSO and water is probed by intermolecular NOE measurements. The NOE effects are interpreted in terms of specific binding of the solvent to certain sites of the molecules. It is shown that DMSO attaches to specific sites of the sucrose molecule, whereas for water such a clear differentiation cannot be proven. (author)

  9. Microscopic picture of the aqueous solvation of glutamic acid

    NARCIS (Netherlands)

    Leenders, E.J.M.; Bolhuis, P.G.; Meijer, E.J.

    2008-01-01

    We present molecular dynamics simulations of glutamic acid and glutamate solvated in water, using both density functional theory (DFT) and the Gromos96 force field. We focus on the microscopic aspects of the solvation−particularly on the hydrogen bond structures and dynamics−and investigate the

  10. On the coupling between molecular diffusion and solvation shell exchange

    DEFF Research Database (Denmark)

    Møller, Klaus Braagaard; Rey, Rossend; Masia, Marco

    2005-01-01

    The connection between diffusion and solvent exchanges between first and second solvation shells is studied by means of molecular dynamics simulations and analytic calculations, with detailed illustrations for water exchange for the Li+ and Na+ ions, and for liquid argon. First, two methods...

  11. Comparison between implicit and hybrid solvation methods for the ...

    Indian Academy of Sciences (India)

    Administrator

    Both implicit solvation method (dielectric polarizable continuum model, DPCM) and hybrid ... the free energy change (ΔGsol) as per the PCM ... Here the gas phase change is written as ΔGg = ΔEelec + ..... bution to the field of electrochemistry.

  12. Polarizability and Aqueous Solvation of the Sulfate Dianion

    Czech Academy of Sciences Publication Activity Database

    Jungwirth, Pavel; Curtis, J. E.; Tobias, D. J.

    2003-01-01

    Roč. 367, - (2003), s. 704-710 ISSN 0009-2614 R&D Projects: GA MŠk LN00A032 Institutional research plan: CEZ:AV0Z4040901 Keywords : polarizability * aqueous solvation * dianion Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.438, year: 2003

  13. Modeling solvation effects in real-space and real-time within density functional approaches

    Energy Technology Data Exchange (ETDEWEB)

    Delgado, Alain [Istituto Nanoscienze - CNR, Centro S3, via Campi 213/A, 41125 Modena (Italy); Centro de Aplicaciones Tecnológicas y Desarrollo Nuclear, Calle 30 # 502, 11300 La Habana (Cuba); Corni, Stefano; Pittalis, Stefano; Rozzi, Carlo Andrea [Istituto Nanoscienze - CNR, Centro S3, via Campi 213/A, 41125 Modena (Italy)

    2015-10-14

    The Polarizable Continuum Model (PCM) can be used in conjunction with Density Functional Theory (DFT) and its time-dependent extension (TDDFT) to simulate the electronic and optical properties of molecules and nanoparticles immersed in a dielectric environment, typically liquid solvents. In this contribution, we develop a methodology to account for solvation effects in real-space (and real-time) (TD)DFT calculations. The boundary elements method is used to calculate the solvent reaction potential in terms of the apparent charges that spread over the van der Waals solute surface. In a real-space representation, this potential may exhibit a Coulomb singularity at grid points that are close to the cavity surface. We propose a simple approach to regularize such singularity by using a set of spherical Gaussian functions to distribute the apparent charges. We have implemented the proposed method in the OCTOPUS code and present results for the solvation free energies and solvatochromic shifts for a representative set of organic molecules in water.

  14. Study of the electron energy distribution function in plasma produced by a rf discharge in a mixture of inert gases

    International Nuclear Information System (INIS)

    Vagner, S.D.; Ignat'ev, B.K.

    1983-01-01

    Electron energy distribution functions (EEDF) are recorded in an rf discharge in a mixture of neon and argon. The rates of different ionization processes and the energy losses of the electrons in the bulk of the discharge are calculated. The experimentally recorded electron energy distribution functions are compared with distributions calculated using a nonlocal theory. The effect of an rf voltage in the probe circuit on the recorded electron energy distribution functions is investigated experimentally

  15. Comparison of the Marcus and Pekar partitions in the context of non-equilibrium, polarizable-continuum solvation models

    International Nuclear Information System (INIS)

    You, Zhi-Qiang; Herbert, John M.; Mewes, Jan-Michael; Dreuw, Andreas

    2015-01-01

    The Marcus and Pekar partitions are common, alternative models to describe the non-equilibrium dielectric polarization response that accompanies instantaneous perturbation of a solute embedded in a dielectric continuum. Examples of such a perturbation include vertical electronic excitation and vertical ionization of a solution-phase molecule. Here, we provide a general derivation of the accompanying polarization response, for a quantum-mechanical solute described within the framework of a polarizable continuum model (PCM) of electrostatic solvation. Although the non-equilibrium free energy is formally equivalent within the two partitions, albeit partitioned differently into “fast” versus “slow” polarization contributions, discretization of the PCM integral equations fails to preserve certain symmetries contained in these equations (except in the case of the conductor-like models or when the solute cavity is spherical), leading to alternative, non-equivalent matrix equations. Unlike the total equilibrium solvation energy, however, which can differ dramatically between different formulations, we demonstrate that the equivalence of the Marcus and Pekar partitions for the non-equilibrium solvation correction is preserved to high accuracy. Differences in vertical excitation and ionization energies are <0.2 eV (and often <0.01 eV), even for systems specifically selected to afford a large polarization response. Numerical results therefore support the interchangeability of the Marcus and Pekar partitions, but also caution against relying too much on the fast PCM charges for interpretive value, as these charges differ greatly between the two partitions, especially in polar solvents

  16. Comparison of the Marcus and Pekar partitions in the context of non-equilibrium, polarizable-continuum solvation models

    Energy Technology Data Exchange (ETDEWEB)

    You, Zhi-Qiang; Herbert, John M., E-mail: herbert@chemistry.ohio-state.edu [Department of Chemistry and Biochemistry, The Ohio State University, Columbus, Ohio 43210 (United States); Mewes, Jan-Michael; Dreuw, Andreas [Interdisciplinary Center for Scientific Computing, Ruprechts-Karls University, Im Neuenheimer Feld 368, 69120 Heidelberg (Germany)

    2015-11-28

    The Marcus and Pekar partitions are common, alternative models to describe the non-equilibrium dielectric polarization response that accompanies instantaneous perturbation of a solute embedded in a dielectric continuum. Examples of such a perturbation include vertical electronic excitation and vertical ionization of a solution-phase molecule. Here, we provide a general derivation of the accompanying polarization response, for a quantum-mechanical solute described within the framework of a polarizable continuum model (PCM) of electrostatic solvation. Although the non-equilibrium free energy is formally equivalent within the two partitions, albeit partitioned differently into “fast” versus “slow” polarization contributions, discretization of the PCM integral equations fails to preserve certain symmetries contained in these equations (except in the case of the conductor-like models or when the solute cavity is spherical), leading to alternative, non-equivalent matrix equations. Unlike the total equilibrium solvation energy, however, which can differ dramatically between different formulations, we demonstrate that the equivalence of the Marcus and Pekar partitions for the non-equilibrium solvation correction is preserved to high accuracy. Differences in vertical excitation and ionization energies are <0.2 eV (and often <0.01 eV), even for systems specifically selected to afford a large polarization response. Numerical results therefore support the interchangeability of the Marcus and Pekar partitions, but also caution against relying too much on the fast PCM charges for interpretive value, as these charges differ greatly between the two partitions, especially in polar solvents.

  17. A linear solvation energy relationship model of organic chemical partitioning to dissolved organic carbon.

    Science.gov (United States)

    Kipka, Undine; Di Toro, Dominic M

    2011-09-01

    Predicting the association of contaminants with both particulate and dissolved organic matter is critical in determining the fate and bioavailability of chemicals in environmental risk assessment. To date, the association of a contaminant to particulate organic matter is considered in many multimedia transport models, but the effect of dissolved organic matter is typically ignored due to a lack of either reliable models or experimental data. The partition coefficient to dissolved organic carbon (K(DOC)) may be used to estimate the fraction of a contaminant that is associated with dissolved organic matter. Models relating K(DOC) to the octanol-water partition coefficient (K(OW)) have not been successful for many types of dissolved organic carbon in the environment. Instead, linear solvation energy relationships are proposed to model the association of chemicals with dissolved organic matter. However, more chemically diverse K(DOC) data are needed to produce a more robust model. For humic acid dissolved organic carbon, the linear solvation energy relationship predicts log K(DOC) with a root mean square error of 0.43. Copyright © 2011 SETAC.

  18. Molecular dynamics study of thermodynamic stability and dynamics of [Li(glyme)]+ complex in lithium-glyme solvate ionic liquids

    Science.gov (United States)

    Shinoda, Wataru; Hatanaka, Yuta; Hirakawa, Masashi; Okazaki, Susumu; Tsuzuki, Seiji; Ueno, Kazuhide; Watanabe, Masayoshi

    2018-05-01

    Equimolar mixtures of glymes and organic lithium salts are known to produce solvate ionic liquids, in which the stability of the [Li(glyme)]+ complex plays an important role in determining the ionic dynamics. Since these mixtures have attractive physicochemical properties for application as electrolytes, it is important to understand the dependence of the stability of the [Li(glyme)]+ complex on the ion dynamics. A series of microsecond molecular dynamics simulations has been conducted to investigate the dynamic properties of these solvate ionic liquids. Successful solvate ionic liquids with high stability of the [Li(glyme)]+ complex have been shown to have enhanced ion dynamics. Li-glyme pair exchange rarely occurs: its characteristic time is longer than that of ion diffusion by one or two orders of magnitude. Li-glyme pair exchange most likely occurs through cluster formation involving multiple [Li(glyme)]+ pairs. In this process, multiple exchanges likely take place in a concerted manner without the production of energetically unfavorable free glyme or free Li+ ions.

  19. Dislocation Loops with a Burgers Vector Produced by 1 MeV Electron Irradiation in FCC Copper-Nickel

    DEFF Research Database (Denmark)

    Leffers, Torben; Barlow, P.

    1975-01-01

    Dislocation loops with Burgers vector a are formed in Cu-Ni alloys during 1 MeV electron irradiation in a high-voltage electron microscope at 350°-400°C. The dislocation loops are of interstitial type and pure edge in character with line vectors. Some of the loops are seen to dissociate into loop...

  20. Installation And Test Of Electron Beam Generation System To Produce Far-Infrared Radiation And X-Ray Pulses

    International Nuclear Information System (INIS)

    Wichaisirimongkol, Pathom; Jinamoon, Witoon; Khangrang, Nopadon; Kusoljariyakul, Keerati; Rhodes, Michael W.; Rimjaem, Sakhorn; Saisut, Jatuporn; Chitrlada, Thongbai; Vilaithong, Thiraphat; Wiedemann, Helmut

    2005-10-01

    SURIYA project at the Fast Neutron Research Facility, Chiang Mai University, aims to establish a facility to generate femtosecond electron beams. This electron beam can be used to generate high intensity far-infrared radiation and ultra-short X-ray pulses. The main components of the system are a 3 MeV RF electron gun with a thermionic cathode, an a-magnet as a bunch compressor, and post acceleration 15-20 MeV by a linear accelerator (linac). Between the main components, there are focusing quadrupole magnets and steering magnets to maintain the electron beam within a high vacuum tube. At the end of the beam transport line, a dipole magnet has been installed to function as a beam dump and an energy spectrometer. After the installation and testing of individual major components were completed, we have been investigating the generation of the electron beam, intense far- infrared radiation and ultra short X-ray pulses

  1. Bone ingrowth potential of electron beam and selective laser melting produced trabecular-like implant surfaces with and without a biomimetic coating

    NARCIS (Netherlands)

    Biemond, J.E.; Hannink, G.; Verdonschot, Nicolaas Jacobus Joseph; Buma, P.

    2013-01-01

    The bone ingrowth potential of trabecular-like implant surfaces produced by either selective laser melting (SLM) or electron beam melting (EBM), with or without a biomimetic calciumphosphate coating, was examined in goats. For histological analysis and histomorphometry of bone ingrowth depth and

  2. Anisotropy enhanced X-ray scattering from solvated transition metal complexes

    DEFF Research Database (Denmark)

    Biasin, Elisa; van Driel, Tim B.; Levi, Gianluca

    2018-01-01

    Time-resolved X-ray scattering patterns from photoexcited molecules in solution are in many cases anisotropic at the ultrafast time scales accessible at X-ray free-electron lasers (XFELs). This anisotropy arises from the interaction of a linearly polarized UV-Vis pump laser pulse with the sample......, which induces anisotropic structural changes that can be captured by femtosecond X-ray pulses. In this work, a method for quantitative analysis of the anisotropic scattering signal arising from an ensemble of molecules is described, and it is demonstrated how its use can enhance the structural...... sensitivity of the time-resolved X-ray scattering experiment. This method is applied on time-resolved X-ray scattering patterns measured upon photoexcitation of a solvated di-platinum complex at an XFEL, and the key parameters involved are explored. It is shown that a combined analysis of the anisotropic...

  3. Hydroxide diffuses slower than hydronium in water because its solvated structure inhibits correlated proton transfer

    Science.gov (United States)

    Chen, Mohan; Zheng, Lixin; Santra, Biswajit; Ko, Hsin-Yu; DiStasio, Robert A., Jr.; Klein, Michael L.; Car, Roberto; Wu, Xifan

    2018-03-01

    Proton transfer via hydronium and hydroxide ions in water is ubiquitous. It underlies acid-base chemistry, certain enzyme reactions, and even infection by the flu. Despite two centuries of investigation, the mechanism underlying why hydroxide diffuses slower than hydronium in water is still not well understood. Herein, we employ state-of-the-art density-functional-theory-based molecular dynamics—with corrections for non-local van der Waals interactions, and self-interaction in the electronic ground state—to model water and hydrated water ions. At this level of theory, we show that structural diffusion of hydronium preserves the previously recognized concerted behaviour. However, by contrast, proton transfer via hydroxide is less temporally correlated, due to a stabilized hypercoordination solvation structure that discourages proton transfer. Specifically, the latter exhibits non-planar geometry, which agrees with neutron-scattering results. Asymmetry in the temporal correlation of proton transfer leads to hydroxide diffusing slower than hydronium.

  4. On the relation between Marcus theory and ultrafast spectroscopy of solvation kinetics

    Science.gov (United States)

    Roy, Santanu; Galib, Mirza; Schenter, Gregory K.; Mundy, Christopher J.

    2018-01-01

    The phenomena of solvent exchange control the process of solvating ions, protons, and charged molecules. Building upon our extension of Marcus' philosophy of electron transfer, we provide a new perspective of ultrafast solvent exchange mechanism around ions measurable by two-dimensional infrared (2DIR) spectroscopy. In this theory, solvent rearrangement drives an ion-bound water to an activated state of higher coordination number, triggering ion-water separation that leads to the solvent-bound state of the water molecule. This ion-bound to solvent-bound transition rate for a BF4--water system is computed using ab initio molecular dynamics and Marcus theory, and is found to be in excellent agreement with the 2DIR measurement.

  5. Monte-Carlo calculations of forward directed bremsstrahlung produced by 20 and 45 MeV electrons on tungsten

    International Nuclear Information System (INIS)

    Goosman, D.R.

    1983-01-01

    The SANDYL Monte-Carlo code has been used to calculate the Bremsstrahlung photon production from beams of parallel electrons incident upon three target geometries. These are 20 MeV electrons onto 1 mm of tungsten + 59 mm of Be, which simulates the operating parameters of the FXR electron accelerator at LLNL Bldg. 801, 45 MeV electrons onto 1 mm of tungsten, and finally 45 MeV electrons onto 1 mm of tungsten and 147 mm of Be. The latter two situations simulate possible future modifications to the FXR accelerator. Graphs of the spectral shape of the Bremsstrahlung photons emitted with angles between 0 0 and 1 0 to the electron direction, the angular distribution of photon-MeV, and the dose reduction curves for each of the three geometries are given. The latter dose reduction curves allow one to calculate forward-directed photon fluxes in real-life situations where the electron beam has non-zero angular divergence

  6. Tris[2-(deuteriomethylsulfanylphenyl]phosphine deuteriochloroform 0.125-solvate

    Directory of Open Access Journals (Sweden)

    Seik Weng Ng

    2008-05-01

    Full Text Available The title deuterated tripodal phosphine, C21H12D9PS3·0.125CDCl3, crystallizes as two independent molecules, one of which lies on a general position and the other about a threefold rotation axis, and as a deuteriochloroform solvate. The solvent molecule is disordered about a site of symmetry 3, so that the ratio of phosphine to solvent is 8:1. The P atom adopts a pyramidal coordination geometry.

  7. Solvation dynamics of lithium salts in wet nitrobenzene

    Czech Academy of Sciences Publication Activity Database

    Moakes, G.; Gelbaum, L. T.; Leisen, J.; Janata, J.; Mareček, Vladimír

    2006-01-01

    Roč. 593, 1-2 (2006), s. 111-118 ISSN 0022-0728 R&D Projects: GA ČR GA203/03/0822 Grant - others:Georgia Research Alliance(US) GRA.CG06.D Institutional research plan: CEZ:AV0Z40400503 Keywords : solvation * NMR * FTIR * nitrobenzene/water * solvatomers Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.339, year: 2006

  8. Experimental studies on the production and suppression mechanism of the hot electrons produced by short wavelength laser

    International Nuclear Information System (INIS)

    Qi Lanying; Jiang Xiaohua; Zhao Xuewei; Li Sanwei; Zhang Wenhai; Li Chaoguang; Zheng Zhijian; Ding Yongkun

    1999-12-01

    The experiments on gold-disk and hohlraum and plastic hydrocarbon (CH) film targets irradiated by laser beams with wavelength 0.35 μm (Xingguang-II) and 0.53 μm (Shenguang-I) are performed. The characteristics of hot electrons are commonly deduced from spectrum of hard X-ray. Associated with the measurement of backward SRS and 3/2ω 0 , the production mechanism of hot electrons for different target type is analyzed in laser plasma with shorter wavelength. A effective way to suppress hot electrons has been found

  9. Backward ejected electrons produced by 1-MeV/u Oq+ (q=3--8) projectile ions colliding with argon gas

    International Nuclear Information System (INIS)

    Breinig, M.; Berryman, J.W.; Segner, F.; Desai, D.D.

    1994-01-01

    The cross sections for ejecting electrons into a cone of half-angle ∼2 degree centered on the backward direction have been measured as a function of electron energy for 1-MeV/u O q+ (q=3--8) projectiles colliding with Ar. For O 3+ and O 4+ projectiles, the cross sections have also been measured in coincidence with exit charge states (q+1) and (q+2) of the projectile. A prominent feature in all spectra is a target LMM Auger peak. The cross sections for producing Ar LMM Auger electrons are nearly independent of projectile incident charge states. A projectile electron-loss peak is produced when the projectile brings loosely bound L-shell electrons into the collision. The shape of this peak is independent of the projectile exit charge state within experimental error. The measured electron-loss production cross sections at 180 degree are compared with the predictions of various on-shell approximations to the impulse approximation. Peak height and position are sensitive functions of the on-shell approximation used. The predictions of the elastic scattering model agree well with the data

  10. A comparison of rat SPECT images obtained using 99mTc derived from 99Mo produced by an electron accelerator with that from a reactor

    International Nuclear Information System (INIS)

    Galea, R; Ross, C K; Moore, K; Wells, R G; Lockwood, J; Harvey, J T; Isensee, G H

    2013-01-01

    Recent shortages of molybdenum-99 ( 99 Mo) have led to an examination of alternate production methods that could contribute to a more robust supply. An electron accelerator and the photoneutron reaction were used to produce 99 Mo from which technetium-99m ( 99m Tc) is extracted. SPECT images of rat anatomy obtained using the accelerator-produced 99m Tc with those obtained using 99m Tc from a commercial generator were compared. Disks of 100 Mo were irradiated with x-rays produced by a 35 MeV electron beam to generate about 1110 MBq (30 mCi) of 99 Mo per disk. After target dissolution, a NorthStar ARSII unit was used to separate the 99m Tc, which was subsequently used to tag pharmaceuticals suitable for cardiac and bone imaging. SPECT images were acquired for three rats and compared to images for the same three rats obtained using 99m Tc from a standard reactor 99 Mo generator. The efficiency of 99 Mo– 99m Tc separation was typically greater than 90%. This study demonstrated the delivery of 99m Tc from the end of beam to the end user of approximately 30 h. Images obtained using the heart and bone scanning agents using reactor and linac-produced 99m Tc were comparable. High-power electron accelerators are an attractive option for producing 99 Mo on a national scale. (paper)

  11. Improvements to the APBS biomolecular solvation software suite.

    Science.gov (United States)

    Jurrus, Elizabeth; Engel, Dave; Star, Keith; Monson, Kyle; Brandi, Juan; Felberg, Lisa E; Brookes, David H; Wilson, Leighton; Chen, Jiahui; Liles, Karina; Chun, Minju; Li, Peter; Gohara, David W; Dolinsky, Todd; Konecny, Robert; Koes, David R; Nielsen, Jens Erik; Head-Gordon, Teresa; Geng, Weihua; Krasny, Robert; Wei, Guo-Wei; Holst, Michael J; McCammon, J Andrew; Baker, Nathan A

    2018-01-01

    The Adaptive Poisson-Boltzmann Solver (APBS) software was developed to solve the equations of continuum electrostatics for large biomolecular assemblages that have provided impact in the study of a broad range of chemical, biological, and biomedical applications. APBS addresses the three key technology challenges for understanding solvation and electrostatics in biomedical applications: accurate and efficient models for biomolecular solvation and electrostatics, robust and scalable software for applying those theories to biomolecular systems, and mechanisms for sharing and analyzing biomolecular electrostatics data in the scientific community. To address new research applications and advancing computational capabilities, we have continually updated APBS and its suite of accompanying software since its release in 2001. In this article, we discuss the models and capabilities that have recently been implemented within the APBS software package including a Poisson-Boltzmann analytical and a semi-analytical solver, an optimized boundary element solver, a geometry-based geometric flow solvation model, a graph theory-based algorithm for determining pK a values, and an improved web-based visualization tool for viewing electrostatics. © 2017 The Protein Society.

  12. Enthalpy-entropy compensation: the role of solvation.

    Science.gov (United States)

    Dragan, Anatoliy I; Read, Christopher M; Crane-Robinson, Colyn

    2017-05-01

    Structural modifications to interacting systems frequently lead to changes in both the enthalpy (heat) and entropy of the process that compensate each other, so that the Gibbs free energy is little changed: a major barrier to the development of lead compounds in drug discovery. The conventional explanation for such enthalpy-entropy compensation (EEC) is that tighter contacts lead to a more negative enthalpy but increased molecular constraints, i.e., a compensating conformational entropy reduction. Changes in solvation can also contribute to EEC but this contribution is infrequently discussed. We review long-established and recent cases of EEC and conclude that the large fluctuations in enthalpy and entropy observed are too great to be a result of only conformational changes and must result, to a considerable degree, from variations in the amounts of water immobilized or released on forming complexes. Two systems exhibiting EEC show a correlation between calorimetric entropies and local mobilities, interpreted to mean conformational control of the binding entropy/free energy. However, a substantial contribution from solvation gives the same effect, as a consequence of a structural link between the amount of bound water and the protein flexibility. Only by assuming substantial changes in solvation-an intrinsically compensatory process-can a more complete understanding of EEC be obtained. Faced with such large, and compensating, changes in the enthalpies and entropies of binding, the best approach to engineering elevated affinities must be through the addition of ionic links, as they generate increased entropy without affecting the enthalpy.

  13. Thermodynamic functions of ion solvation in normal alcohols of aliphatic series

    International Nuclear Information System (INIS)

    Sergeeva, I.A.

    1978-01-01

    Thermodynamic functions of ion solvation of alkali, alkaline earth metals and halogenides in 9 alcohols are calculated using the earlier suggested method. It is shown that summary values are in good accord with experimental ones, the deviations do not surpass 0-5%, solvation energies of one and the same electrolyte in the series of n-alcohols do not change, enthalpy and entropy of solvation increase from lower alcohols to higher ones

  14. Multiple time step molecular dynamics in the optimized isokinetic ensemble steered with the molecular theory of solvation: Accelerating with advanced extrapolation of effective solvation forces

    International Nuclear Information System (INIS)

    Omelyan, Igor; Kovalenko, Andriy

    2013-01-01

    We develop efficient handling of solvation forces in the multiscale method of multiple time step molecular dynamics (MTS-MD) of a biomolecule steered by the solvation free energy (effective solvation forces) obtained from the 3D-RISM-KH molecular theory of solvation (three-dimensional reference interaction site model complemented with the Kovalenko-Hirata closure approximation). To reduce the computational expenses, we calculate the effective solvation forces acting on the biomolecule by using advanced solvation force extrapolation (ASFE) at inner time steps while converging the 3D-RISM-KH integral equations only at large outer time steps. The idea of ASFE consists in developing a discrete non-Eckart rotational transformation of atomic coordinates that minimizes the distances between the atomic positions of the biomolecule at different time moments. The effective solvation forces for the biomolecule in a current conformation at an inner time step are then extrapolated in the transformed subspace of those at outer time steps by using a modified least square fit approach applied to a relatively small number of the best force-coordinate pairs. The latter are selected from an extended set collecting the effective solvation forces obtained from 3D-RISM-KH at outer time steps over a broad time interval. The MTS-MD integration with effective solvation forces obtained by converging 3D-RISM-KH at outer time steps and applying ASFE at inner time steps is stabilized by employing the optimized isokinetic Nosé-Hoover chain (OIN) ensemble. Compared to the previous extrapolation schemes used in combination with the Langevin thermostat, the ASFE approach substantially improves the accuracy of evaluation of effective solvation forces and in combination with the OIN thermostat enables a dramatic increase of outer time steps. We demonstrate on a fully flexible model of alanine dipeptide in aqueous solution that the MTS-MD/OIN/ASFE/3D-RISM-KH multiscale method of molecular dynamics

  15. 2D imaging X-ray diagnostic for measuring the current density distribution in a wide-area electron beam produced in a multiaperture diode with plasma cathode

    Science.gov (United States)

    Kurkuchekov, V.; Kandaurov, I.; Trunev, Y.

    2018-05-01

    A simple and inexpensive X-ray diagnostic tool was designed for measuring the cross-sectional current density distribution in a low-relativistic pulsed electron beam produced in a source based on an arc-discharge plasma cathode and multiaperture diode-type electron optical system. The beam parameters were as follows: Uacc = 50–110 kV, Ibeam = 20–100 A, τbeam = 0.1–0.3 ms. The beam effective diameter was ca. 7 cm. Based on a pinhole camera, the diagnostic allows one to obtain a 2D profile of electron beam flux distribution on a flat metal target in a single shot. The linearity of the diagnostic system response to the electron flux density was established experimentally. Spatial resolution of the diagnostic was also estimated in special test experiments. The optimal choice of the main components of the diagnostic technique is discussed.

  16. Theoretical analysis and simulation of the influence of self-bunching effects and longitudinal space charge effects on the propagation of keV electron bunch produced by a novel S-band Micro-Pulse electron Gun

    Science.gov (United States)

    Zhao, Jifei; Lu, Xiangyang; Zhou, Kui; Yang, Ziqin; Yang, Deyu; Luo, Xing; Tan, Weiwei; Yang, Yujia

    2016-06-01

    As an important electron source, Micro-Pulse electron Gun (MPG) which is qualified for producing high average current, short pulse, low emittance electron bunches steadily holds promise to use as an electron source of Coherent Smith-Purcell Radiation (CSPR), Free Electron Laser (FEL). The stable output of S-band MPG has been achieved in many labs. To establish reliable foundation for the future application of it, the propagation of picosecond electron bunch produced by MPG should be studied in detail. In this article, the MPG which was working on the rising stage of total effective Secondary Electron Yield (SEY) curve was introduced. The self-bunching mechanism was discussed in depth both in the multipacting amplifying state and the steady working state. The bunch length broadening induced by the longitudinal space-charge (SC) effects was investigated by different theoretical models in different regions. The 2D PIC codes MAGIC and beam dynamic codes TraceWin simulations were also performed in the propagation. The result shows an excellent agreement between the simulation and the theoretical analysis for bunch length evolution.

  17. Theoretical analysis and simulation of the influence of self-bunching effects and longitudinal space charge effects on the propagation of keV electron bunch produced by a novel S-band Micro-Pulse electron Gun

    Energy Technology Data Exchange (ETDEWEB)

    Zhao, Jifei; Lu, Xiangyang, E-mail: xylu@pku.edu.cn; Yang, Ziqin; Yang, Deyu; Tan, Weiwei; Yang, Yujia [Institute of Heavy Ion Physics, School of Physics, Peking University, Beijing, 100871 (China); Zhou, Kui; Luo, Xing [Institute of Applied Electronics, China Academy of Engineering Physics, Mianyang 621900 (China)

    2016-06-15

    As an important electron source, Micro-Pulse electron Gun (MPG) which is qualified for producing high average current, short pulse, low emittance electron bunches steadily holds promise to use as an electron source of Coherent Smith-Purcell Radiation (CSPR), Free Electron Laser (FEL). The stable output of S-band MPG has been achieved in many labs. To establish reliable foundation for the future application of it, the propagation of picosecond electron bunch produced by MPG should be studied in detail. In this article, the MPG which was working on the rising stage of total effective Secondary Electron Yield (SEY) curve was introduced. The self-bunching mechanism was discussed in depth both in the multipacting amplifying state and the steady working state. The bunch length broadening induced by the longitudinal space-charge (SC) effects was investigated by different theoretical models in different regions. The 2D PIC codes MAGIC and beam dynamic codes TraceWin simulations were also performed in the propagation. The result shows an excellent agreement between the simulation and the theoretical analysis for bunch length evolution.

  18. Theoretical analysis and simulation of the influence of self-bunching effects and longitudinal space charge effects on the propagation of keV electron bunch produced by a novel S-band Micro-Pulse electron Gun

    Directory of Open Access Journals (Sweden)

    Jifei Zhao

    2016-06-01

    Full Text Available As an important electron source, Micro-Pulse electron Gun (MPG which is qualified for producing high average current, short pulse, low emittance electron bunches steadily holds promise to use as an electron source of Coherent Smith-Purcell Radiation (CSPR, Free Electron Laser (FEL. The stable output of S-band MPG has been achieved in many labs. To establish reliable foundation for the future application of it, the propagation of picosecond electron bunch produced by MPG should be studied in detail. In this article, the MPG which was working on the rising stage of total effective Secondary Electron Yield (SEY curve was introduced. The self-bunching mechanism was discussed in depth both in the multipacting amplifying state and the steady working state. The bunch length broadening induced by the longitudinal space-charge (SC effects was investigated by different theoretical models in different regions. The 2D PIC codes MAGIC and beam dynamic codes TraceWin simulations were also performed in the propagation. The result shows an excellent agreement between the simulation and the theoretical analysis for bunch length evolution.

  19. Relativistic electron dynamics produced by azimuthally localized poloidal mode ULF waves: Boomerang-shaped pitch angle evolutions

    Science.gov (United States)

    Hao, Y.; Zong, Q.; Zhou, X.; Rankin, R.; Chen, X.; Liu, Y.; Fu, S.; Spence, H. E.; Blake, J. B.; Reeves, G. D.

    2017-12-01

    We present an analysis of "boomerang-shaped" pitch angle evolutions of outer radiation belt relativistic electrons observed by the Van Allen Probes after the passage of an interplanetary shock on June 7th, 2014. The flux at different pitch angles is modulated by Pc5 waves, with equatorially mirroring electrons reaching the satellite first. For 90º pitch angle electrons, the phase change of the flux modulations across energy exceeds 180º, and increasingly tilts with time. Using estimates of the arrival time of particles of different pitch angles at the spacecraft location, a scenario is investigated in which shock-induced ULF waves interact with electrons through the drift resonance mechanism in a localized region westward of the spacecraft. Numerical calculations on particle energy gain with the modified ULF wave field reproduce the observed boomerang stripes and modulations in the electron energy spectrogram. The study of boomerang stripes and their relationship to drift-resonance taking place at a location different from the observation point adds new understanding of the processes controlling the dynamics of the outer radiation belt.

  20. Relativistic electron dynamics produced by azimuthally localized poloidal mode ULF waves: Boomerang-shaped pitch angle evolutions

    International Nuclear Information System (INIS)

    Hao, Y. X.; Zong, Q.-G.; Zhou, X.-Z.; Rankin, R.; Chen, X. R.

    2017-01-01

    Here, we present an analysis of “boomerang-shaped” pitch angle evolutions of outer radiation belt relativistic electrons observed by the Van Allen Probes after the passage of an interplanetary shock on 7 June 2014. The flux at different pitch angles is modulated by Pc5 waves, with equatorially mirroring electrons reaching the satellite first. For 90° pitch angle electrons, the phase change of the flux modulations across energy exceeds 180° and increasingly tilts with time. Using estimates of the arrival time of particles of different pitch angles at the spacecraft location, a scenario is investigated in which shock-induced ULF waves interact with electrons through the drift resonance mechanism in a localized region westward of the spacecraft. Numerical calculations on particle energy gain with the modified ULF wavefield reproduce the observed boomerang stripes and modulations in the electron energy spectrogram. The study of boomerang stripes and their relationship to drift resonance taking place at a location different from the observation point adds new understanding of the processes controlling the dynamics of the outer radiation belt.

  1. Coulomb focusing and ''path'' interference of autoionizing electrons produced in 10 keV He+ + He collisions

    International Nuclear Information System (INIS)

    Swenson, J.K.; Burgdoerfer, J.; Meyer, F.W.; Havener, C.C.; Gregory, D.C.; Stolterfoht, N.

    1991-01-01

    Autoionizing electrons emitted following low energy ion-atom collisions may scatter significantly from the receding spectator ion's attractive Coulomb field. In such cases the observed electron intensity is ''focused'' in the direction of the scattering ion as a result of the effective compression of the emission solid angle. In addition, interference may occur between trajectories, corresponding to electrons scattering around opposite sides of the ion, which lead to the same final laboratory electron energy and emission angle. This Coulomb ''path'' interference mechanism manifests itself in the uncharacteristically rapid angular dependence of the He target 2s 2 1 S autoionizing state measured near 0 degree following low energy He + + He collisions. A classical trajectory model for Coulomb focusing is presented and a semi-classical approximation is used to model the Coulomb ''path'' interference mechanism. In this description we account for the evolution of the phase of the autoionizing state until its decay and the path dependence of the amplitude of the emitted electron following decay of the autoionizing state. Calculated model lineshapes, which include contributions from adjacent overlapping resonances, reproduce quite well the angular dependence observed in the data near 0 degree. 14 refs., 7 figs

  2. Studies of dislocation loops produced by irradiation of ZnO in a high-voltage electron microscope

    International Nuclear Information System (INIS)

    Yoshiie, T.; Iwanaga, H.; Shibata, N.; Suzuki, K.; Takeuchi, S.

    1980-01-01

    Electron-irradiation studies on vapour-grown ZnO ribbon crystals have been carried out in situ in a high-voltage electron microscope. Dislocation loops nucleate both on stacking-fault planes and in the matrix by irradiation with electron accelerated through voltages higher than 700 kV at room temperature. Two types of loops with the Burgers vectors b=1/2c and b=a exist in the matrix, where a=1/3 and c=[0001]. On the other hand, loops with b=1/2c+a/3 and those with b=1/2c are formed on the prismatic fault planes and basal fault planes, respectively. Diffraction-contrast experiments show these loops to be of interstitial type. A re-irradiation experiment after the annealing indicates a possibility that there exist vacancies in the matrix at 700 0 C. (author)

  3. The usage of electron beam to produce radio isotopes through the uranium fission by γ-rays and neutrons

    International Nuclear Information System (INIS)

    Bunatyan, G.G.; Nikolenko, V.G.; Popov, A.V.

    2010-01-01

    We treat the production of desirable radio isotopes due to the 238 U photo-fission by the bremsstrahlung induced in converter by an initial electron beam provided by a linear electron accelerator. We consider as well the radio isotope production through the 238 U fission by the neutrons that stem in the 238 U sample irradiated by that bremsstrahlung. The yield of the most applicable radio isotope 99 Mo is calculated. We correlate the findings acquired in the work presented with those obtained by treating the nuclear photo-neutron reaction. Menace of the plutonium contamination of an irradiated uranium sample because of the neutron capture by 238 U is considered. As we get convinced, the photo-neutron production of radio isotopes proves to be more practicable than the production by the uranium photo- and neutron-fission. Both methods are certain to be brought into action due to usage of the electron beam provided by modern linear accelerators

  4. Stable, tunable, quasimonoenergetic electron beams produced in a laser wakefield near the threshold for self-injection

    Directory of Open Access Journals (Sweden)

    S. Banerjee

    2013-03-01

    Full Text Available Stable operation of a laser-plasma accelerator near the threshold for electron self-injection in the blowout regime has been demonstrated with 25–60 TW, 30 fs laser pulses focused into a 3–4 millimeter length gas jet. Nearly Gaussian shape and high nanosecond contrast of the focused pulse appear to be critically important for controllable, tunable generation of 250–430 MeV electron bunches with a low-energy spread, ∼10  pC charge, a few-mrad divergence and pointing stability, and a vanishingly small low-energy background. The physical nature of the near-threshold behavior is examined using three-dimensional particle-in-cell simulations. Simulations indicate that properly locating the nonlinear focus of the laser pulse within the plasma suppresses continuous injection, thus reducing the low-energy tail of the electron beam.

  5. The influence of defects produced by high energy electrons on the electrical characteristics of p-n junctions

    International Nuclear Information System (INIS)

    Koch, L.; Van Dong, N.

    1961-01-01

    The life-time of minority carriers in semi-conductors is very sensitive to the presence of defects introduced by high-energy electrons. The formation of defects thus affects the short-circuiting current and the open circuit voltage of a p-n junction, these being dependent on the life-time. In the work presented, we have bombarded several types of germanium and silicon junctions with 2 MeV electrons from a Van der Graaff, and with β-particles from radioactive sources. The experiments were carried out both at ordinary temperatures and that of liquid air. In this latter case an anomaly in the electron-volt effect was found: the short-circuiting current and the voltage in vacuo, after an initial decrease, increase again and exceed their initial maximum value before once more decreasing. A qualitative interpretation of this abnormal effect is given. (author) [fr

  6. A Monte Carlo Code (PHOEL) for generating initial energies of photoelectrons and compton electrons produced by photons in water

    International Nuclear Information System (INIS)

    Turner, J.E.; Modolo, J.T.; Sordi, G.M.A.A.; Hamm, R.N.; Wright, H.A.

    1979-01-01

    PHOEL provides a source term for a Monte Carlo code which calculates the electron transport and energy degradation in liquid water. This code is used to study the relative biological effectiveness (RBE) of low-LET radiation at low doses. The basic numerical data used and their mathematical treatment are described as well as the operation of the code [pt

  7. Optical and energy dependent response of the alanine gel solution produced at IPEN to clinical photons and electrons beams

    International Nuclear Information System (INIS)

    Silva, Cleber F.

    2011-01-01

    The DL-Alanine (C 3 H 7 NO 2 ) is an amino acid tissue equivalent traditionally used as standard dosimetric material in EPR dosimetry. Recently, it has been studied to be applied in gel dosimetry, considering that the addition of Alanine in the Fricke gel solution improves the production of ferric ions radiation induced. The spectrophotometric evaluation technique can be used comparing the two spectrum wavelengths bands: 457 nm band that corresponds to ferrous ions and 588 nm band that corresponds to ferric ions concentration to evaluate the dosimetric properties of this material. The performance of the Alanine gel solution developed at IPEN has been firstly studied using the spectrophotometric technique aiming to apply this material to 3D clinical doses evaluations using MRI technique. In this work, the optical and the energy dependent response of this solution submitted to clinical photons and electrons beams were studied. Different batches of gel solutions were prepared and maintained at low temperature during 12 h to solidification. Before irradiation, the samples were maintained during 1 h at room temperature. The photons and electrons irradiations were carried out using a Varian 2100C Medical Linear Accelerator of the Radiotherapy Department of the Hospital das Clinicas of the University of Sao Paulo with absorbed doses between 1 and 40 Gy; radiation field of 10 x 10 cm 2 ; photon energies of 6 MeV and 15 MeV; and electron with energies between 6 and 15 MeV. The obtained results indicate that signal response dependence for clinical photons and electrons beams, to the same doses, for Alanine gel dosimeter is better than 3.6 % (1σ), and the energy dependence response, to the same doses, is better 3% (1σ) for both beams. These results indicate that the same calibration factor can be used and the optical response is energy independent in the studied dose range and clinical photons and electrons beams energies. (author)

  8. Device for irradiation of a target surface by a variable electron beam, especially electron beam generator, in order to produce semiconductor components

    International Nuclear Information System (INIS)

    Wolfe, J.E.

    1978-01-01

    For the lithographic device there is used a field emission source for thermal ions with a tungsten cathode and a zirconium top as an electron gain. For production of IC chips the electron beam of 1000 A/cm 2 can be focused on a mask template, mounted on a x/Y table, by means of a system of lenses. The electromagnetic focusing device with a small aberration coefficient is designed in such a way that there is obtained a large focal length on the image side as compared to the focal length on the object side. Thereby a small angular deflection of the beam in the focusing device causes a large deflection at the target. The control is performed by a processor. (RW) [de

  9. A polarizable QM/MM approach to the molecular dynamics of amide groups solvated in water

    Energy Technology Data Exchange (ETDEWEB)

    Schwörer, Magnus; Wichmann, Christoph; Tavan, Paul, E-mail: tavan@physik.uni-muenchen.de [Lehrstuhl für BioMolekulare Optik, Ludwig-Maximilians Universität München, Oettingenstr. 67, 80538 München (Germany)

    2016-03-21

    The infrared (IR) spectra of polypeptides are dominated by the so-called amide bands. Because they originate from the strongly polar and polarizable amide groups (AGs) making up the backbone, their spectral positions sensitively depend on the local electric fields. Aiming at accurate computations of these IR spectra by molecular dynamics (MD) simulations, which derive atomic forces from a hybrid quantum and molecular mechanics (QM/MM) Hamiltonian, here we consider the effects of solvation in bulk liquid water on the amide bands of the AG model compound N-methyl-acetamide (NMA). As QM approach to NMA we choose grid-based density functional theory (DFT). For the surrounding MM water, we develop, largely based on computations, a polarizable molecular mechanics (PMM) model potential called GP6P, which features six Gaussian electrostatic sources (one induced dipole, five static partial charge distributions) and, therefore, avoids spurious distortions of the DFT electron density in hybrid DFT/PMM simulations. Bulk liquid GP6P is shown to have favorable properties at the thermodynamic conditions of the parameterization and beyond. Lennard-Jones (LJ) parameters of the DFT fragment NMA are optimized by comparing radial distribution functions in the surrounding GP6P liquid with reference data obtained from a “first-principles” DFT-MD simulation. Finally, IR spectra of NMA in GP6P water are calculated from extended DFT/PMM-MD trajectories, in which the NMA is treated by three different DFT functionals (BP, BLYP, B3LYP). Method-specific frequency scaling factors are derived from DFT-MD simulations of isolated NMA. The DFT/PMM-MD simulations with GP6P and with the optimized LJ parameters then excellently predict the effects of aqueous solvation and deuteration observed in the IR spectra of NMA. As a result, the methods required to accurately compute such spectra by DFT/PMM-MD also for larger peptides in aqueous solution are now at hand.

  10. Electron spin resonance and E.N.D.O.R. double resonance study of free radicals produced by gamma irradiation of imidazole single crystals

    International Nuclear Information System (INIS)

    Lamotte, B.

    1970-01-01

    Gamma irradiation of imidazole single crystals at 300 deg. K gives two radicals. Identification and detailed studies of their electronic and geometric structure have been made by ESR and ENDOR techniques. A study of the hydrogen bonded protons hyperfine tensor is made and let us conclude to the inexistence of movement and tunneling of these protons. The principal low temperature radical, produced by gamma irradiation at 77 deg. K has been also studied by ESR and a model has been proposed. (author) [fr

  11. Simulation of electron density disturbances of the ionospheric D region produced by high-energy particle fluxes

    International Nuclear Information System (INIS)

    Martynenko, S.I.

    1989-01-01

    Using the large-scale tim expansion analytical solutions of electron concentration balance equation in D-region of the ionosphere for pulsed and periodic changes in the rate of ion formatin under the effect of fluxes of precipitating high-energy particles are obtained. Possible effect of disturbances of temperature of nutrals is taken into account. On the basis of model representations the space-time structure of emerging ionospheric disturbances is discussed

  12. Electron spin ressonance of radicals produced by ultra-violet photolysis of KCL dopped with potassium cyanide and potassium cyanate

    International Nuclear Information System (INIS)

    Duran, J.E.R.

    1975-01-01

    The production of radicals by ultra-violet photolysis of KCL dopped with potassium cyanide and potassium cyanate is studied by electron spin resonance. Several new paramagnetic species are detected which are identified as HCNO - , NCN - /NCNO - , CNN - /CNON - and CNOsup(=) all giving isotropic spectra at 77 0 K. The temperature dependence of the CNOsup(=) spectrum is investigated down to 1.6 0 K. It is found that two different recrientation motions ocurr which freeze at different temperatures. The effect of this motion on the line width is analized using Anderson's theory of exchange narrowing. The electronic structure of the CNOsup(=) radical is discussed using the measured the carbon and nitrogen hfs constants. It is found that a bonding scheme similar to that accepted for the isoelectronic molecule NO 2 is applicable, and a one electron molecular orbital scheme is given. Within this scheme a negative contribution to the nitrogen isotropic hfs constant is found which is assumed to originate from the polarization of the fully occupied ls orbitals [pt

  13. Nascent rotational distributions of N+2(X 2Σ+/sub g/) produced by electron-impact ionization of N2 in a supersonic beam

    International Nuclear Information System (INIS)

    Nagata, T.; Nakajima, A.; Kondow, T.; Kuchitsu, K.

    1987-01-01

    Laser-induced fluorescence from nascent N + 2 (X 2 Σ + /sub g/) ions produced by electron impact on a N 2 supersonic beam was observed. An analysis of the B 2 Σ + /sub u/-X 2 Σ + /sub g/ (0,0) band shows that the rotational state distributions cannot be represented by a single Boltzmann function, higher N'' levels being overpopulated. Experimental and analytical efforts were made to minimize the influence of cascading and relaxation on the rotational distributions. The rotational energy of N + 2 (X) thus estimated increases with decreasing electron energy from 2.26 +- 0.16 meV at 300 eV to 4.24 +- 0.27 meV at 25 eV. This trend is explained qualitatively in terms of angular momentum transfer through multipole electron--molecule interactions

  14. Electron beam inactivation of Tulane virus on fresh produce, and mechanism of inactivation of human norovirus surrogates by electron beam irradiation.

    Science.gov (United States)

    Predmore, Ashley; Sanglay, Gabriel C; DiCaprio, Erin; Li, Jianrong; Uribe, R M; Lee, Ken

    2015-04-02

    Ionizing radiation, whether by electron beams or gamma rays, is a non-thermal processing technique used to improve the microbial safety and shelf-life of many different food products. This technology is highly effective against bacterial pathogens, but data on its effect against foodborne viruses is limited. A mechanism of viral inactivation has been proposed with gamma irradiation, but no published study discloses a mechanism for electron beam (e-beam). This study had three distinct goals: 1) evaluate the sensitivity of a human norovirus surrogate, Tulane virus (TV), to e-beam irradiation in foods, 2) compare the difference in sensitivity of TV and murine norovirus (MNV-1) to e-beam irradiation, and 3) determine the mechanism of inactivation of these two viruses by e-beam irradiation. TV was reduced from 7 log10 units to undetectable levels at target doses of 16 kGy or higher in two food matrices (strawberries and lettuce). MNV-1 was more resistant to e-beam treatment than TV. At target doses of 4 kGy, e-beam provided a 1.6 and 1.2 log reduction of MNV-1 in phosphate buffered saline (PBS) and Dulbecco's Modified Eagle Medium (DMEM), compared to a 1.5 and 1.8 log reduction of TV in PBS and Opti-MEM, respectively. Transmission electron microscopy revealed that increased e-beam doses negatively affected the structure of both viruses. Analysis of viral proteins by SDS-PAGE found that irradiation also degraded viral proteins. Using RT-PCR, irradiation was shown to degrade viral genomic RNA. This suggests that the mechanism of inactivation of e-beam was likely the same as gamma irradiation as the damage to viral constituents led to inactivation. Copyright © 2014 Elsevier B.V. All rights reserved.

  15. Solvation quantities from a COSMO-RS equation of state

    International Nuclear Information System (INIS)

    Panayiotou, C.; Tsivintzelis, I.; Aslanidou, D.; Hatzimanikatis, V.

    2015-01-01

    Highlights: • Extension of the successful COSMO-RS model to an equation-of-state model. • Two scaling constants, obtained from atom-specific contributions. • Overall estimation of the solvation quantities and contributions. - Abstract: This work focuses on the extension of the successful COSMO-RS model of mixtures into an equation-of-state model of fluids and its application for the estimation of solvation/hydration quantities of a variety of chemical substances. These quantities include free-energies, enthalpies and entropies of hydration as well as the separate contributions to each of them. Emphasis is given on the estimation of contributions from the conformational changes of solutes upon solvation and the associated restructuring of solvent in its immediate neighborhood. COSMO-RS is a quantum-mechanics based group/segment contribution model in which the Quasi-Chemical (QC) approach is used for the description of the non-random distribution of interacting segments in the system. Thus, the equation-of-state development is done through such a QC framework. The new model will not need any adjustable parameters for the strong specific interactions, such as hydrogen bonds, since they will be provided by the quantum-mechanics based cosmo-files – a key feature of COSMO-RS model. It will need, however, one volumetric and one energy parameter per fluid, which are scaling constants or molecular descriptors of the fluid and are obtained from rather easily available data such as densities, boiling points, vapor pressures, heats of vaporization or second virial coefficients. The performance and the potential of the new equation-of-state model to become a fully predictive model are critically discussed

  16. Molecular dynamics study of the solvation of an alpha-helical transmembrane peptide by DMSO

    NARCIS (Netherlands)

    Duarte, A.M.; Mierlo, van C.P.M.; Hemminga, M.A.

    2008-01-01

    10-ns molecular dynamics study of the solvation of a hydrophobic transmembrane helical peptide in dimethyl sulfoxide (DMSO) is presented. The objective is to analyze how this aprotic polar solvent is able to solvate three groups of amino acid residues (i.e., polar, apolar, and charged) that are

  17. Studies of base pair sequence effects on DNA solvation based on all

    Indian Academy of Sciences (India)

    Detailed analyses of the sequence-dependent solvation and ion atmosphere of DNA are presented based on molecular dynamics (MD) simulations on all the 136 unique tetranucleotide steps obtained by the ABC consortium using the AMBER suite of programs. Significant sequence effects on solvation and ion localization ...

  18. Femtosecond spectroscopic study of the solvation of amphiphilic molecules by water

    NARCIS (Netherlands)

    Rezus, Y.L.A.; Bakker, H.J.

    2008-01-01

    We use polarization-resolved mid-infrared pump-probe spectroscopy to study the aqueous solvation of proline and N-methylacetamide. These molecules serve as models to study the solvation of proteins. We monitor the orientational dynamics of partly deuterated water molecules (HDO) that are present at

  19. Competitive solvation of (bis)(trifluoromethanesulfonyl)imide anion by acetonitrile and water

    DEFF Research Database (Denmark)

    Chaban, Vitaly

    2014-01-01

    Competitive solvation of an ion by two or more solvents is one of the key phenomena determining the identity of our world. Solvation in polar solvents frequently originates from non-additive non-covalent interactions. Pre-parametrized potentials poorly capture these interactions, unless the force...

  20. Time-dependent friction and solvation time correlation function

    International Nuclear Information System (INIS)

    Samanta, Alok; Ali, Sk Musharaf; Ghosh, Swapan K

    2005-01-01

    We have derived a new relation between the time-dependent friction and solvation time correlation function (STCF) for non-polar fluids. The friction values calculated using this relation and simulation results on STCF for a Lennard-Jones fluid are shown to have excellent agreement with the same obtained through mode-coupling theory. Also derived is a relation between the time-dependent dielectric friction and STCF for polar fluids. Routes are thus provided to obtain the time-dependent friction (non-polar as well as dielectric) from an experimentally measured quantity like STCF, even if the interparticle interaction potential is not known

  1. Electrochemical redox reactions in solvated silica sol-gel glass

    International Nuclear Information System (INIS)

    Opallo, M.

    2002-01-01

    The studies of electrochemical redox reactions in solvated silica sol-gel glass were reviewed. The methodology of the experiments with emphasis on the direct preparation of the solid electrolyte and the application ultra microelectrodes was described. Generally, the level of the electrochemical signal is not much below that observed in liquid electrolyte. The current depends on time elapsed after gelation, namely the longer time, the smaller current. The differences between electrochemical behaviour of the redox couples in monoliths and thin layers were described. (author)

  2. Study of the Betatron and Compton X-ray sources produced in laser wakefield acceleration of electrons

    International Nuclear Information System (INIS)

    Ferri, Julien

    2016-01-01

    An ultra-short and ultra-intense laser pulse propagating in a low-density gas can accelerate in its wake a part of the electrons ionized from the gas to relativistic energies of a few hundreds of MeV over distances of a few millimeters only. During their acceleration, as a consequence of their transverse motion, these electrons emit strongly collimated X-rays in the forward direction, which are called betatron radiations. The characteristics of this source turn it into an interesting tool for high-resolution imagery.In this thesis, we explore three different axis to work on this source using simulations on the Particles-In-Cells codes CALDER and CALDER-Circ. We first study the creation of a betatron X-ray source with kilo-joule and pico-second laser pulses, for which duration and energy are then much higher than usual in this domain. In spite of the unusual laser parameters, we show that X-ray sources can still be generated, furthermore in two different regimes.In a second study, the generally observed discrepancies between experiments and simulations are investigated. We show that the use of realistic laser profiles instead of Gaussian ones in the simulations strongly degrades the performances of the laser-plasma accelerator and of the betatron source. Additionally, this leads to a better qualitative and quantitative agreement with the experiment. Finally, with the aim of improving the X-ray emission, we explore several techniques based on the manipulation of the plasma density profile used for acceleration. We find that both the use of a transverse gradient and of a density step increases the amplitude of the electrons transverse motions, and then increases the radiated energy. Alternatively, we show that this goal can also be achieved through the transition from a laser wakefield regime to a plasma wakefield regime induced by an increase of the density. The laser wakefield optimizes the electron acceleration whereas the plasma wakefield favours the X

  3. Electron beam irradiating process for rendering rough or topographically irregular surface substrates smooth; and coated substrates produced thereby

    International Nuclear Information System (INIS)

    Nablo, S.V.

    1979-01-01

    This disclosure involves a novel process for instantaneous electron-beam curing of very thin low viscosity, solventless coating upon rough, irregular or textured surfaces of a substrate such as paper or the like. Through rather critical timing and energy adjustment procedures, the coating firmly adheres to the surface before the coating can conform to the roughness or texture contour or substantially penetrate into the surface. By this method a solidified very smooth outer surface is provided for the substrate that is particularly used for metalization and other finished layerings. (author)

  4. Angular distribution of thick-target bremsstrahlung produced by electrons with initial energies ranging from 10 to 20 keV incident on Ag

    Energy Technology Data Exchange (ETDEWEB)

    Gonzales, D.; Cavness, B.; Williams, S. [Department of Physics, Angelo State University, San Angelo, Texas 76909 (United States)

    2011-11-15

    Experimental results are presented comparing the intensities of the bremsstrahlung produced by electrons with initial energies ranging from 10 to 20 keV incident on a thick Ag target, measured at forward angles in the range of 0 degree sign to 55 degree sign . When the data are corrected for attenuation due to photon absorption within the target, the results indicate that the detected radiation is distributed anisotropically only at photon energies k that are approximately equal to the initial energy of the incident electrons E{sub 0}. The results of our experiments suggest that, as k/E{sub 0}{yields} 0, the detected radiation essentially becomes isotropic due primarily to the scattering of electrons within the target. A comparison to the theory of Kissel et al.[At. Data Nucl. Data Tables 28, 381 (1983)] suggests that the angular distribution of bremsstrahlung emitted by electrons incident on thick targets is similar to the angular distribution of bremsstrahlung emitted by electrons incident on free-atom targets only when k/E{sub 0}{approx_equal} 1. The experimental data also are in approximate agreement with the angular distribution predictions of the Monte Carlo program penelope.

  5. Highly reliable field electron emitters produced from reproducible damage-free carbon nanotube composite pastes with optimal inorganic fillers

    Science.gov (United States)

    Kim, Jae-Woo; Jeong, Jin-Woo; Kang, Jun-Tae; Choi, Sungyoul; Ahn, Seungjoon; Song, Yoon-Ho

    2014-02-01

    Highly reliable field electron emitters were developed using a formulation for reproducible damage-free carbon nanotube (CNT) composite pastes with optimal inorganic fillers and a ball-milling method. We carefully controlled the ball-milling sequence and time to avoid any damage to the CNTs, which incorporated fillers that were fully dispersed as paste constituents. The field electron emitters fabricated by printing the CNT pastes were found to exhibit almost perfect adhesion of the CNT emitters to the cathode, along with good uniformity and reproducibility. A high field enhancement factor of around 10 000 was achieved from the CNT field emitters developed. By selecting nano-sized metal alloys and oxides and using the same formulation sequence, we also developed reliable field emitters that could survive high-temperature post processing. These field emitters had high durability to post vacuum annealing at 950 °C, guaranteeing survival of the brazing process used in the sealing of field emission x-ray tubes. We evaluated the field emitters in a triode configuration in the harsh environment of a tiny vacuum-sealed vessel and observed very reliable operation for 30 h at a high current density of 350 mA cm-2. The CNT pastes and related field emitters that were developed could be usefully applied in reliable field emission devices.

  6. Highly Al-doped TiO{sub 2} nanoparticles produced by Ball Mill Method: structural and electronic characterization

    Energy Technology Data Exchange (ETDEWEB)

    Santos, Desireé M. de los, E-mail: desire.delossantos@uca.es; Navas, Javier, E-mail: javier.navas@uca.es; Sánchez-Coronilla, Antonio; Alcántara, Rodrigo; Fernández-Lorenzo, Concha; Martín-Calleja, Joaquín

    2015-10-15

    Highlights: • Highly Al-doped TiO{sub 2} nanoparticles were synthesized using a Ball Mill Method. • Al doping delayed anatase to rutile phase transformation. • Al doping allow controlling the structural and electronic properties of nanoparticles. - Abstract: This study presents an easy method for synthesizing highly doped TiO{sub 2} nanoparticles. The Ball Mill method was used to synthesize pure and Al-doped titanium dioxide, with an atomic percentage up to 15.7 at.% Al/(Al + Ti). The samples were annealed at 773 K, 973 K and 1173 K, and characterized using ICP-AES, XRD, Raman spectroscopy, FT-IR, TG, STEM, XPS, and UV–vis spectroscopy. The effect of doping and the calcination temperature on the structure and properties of the nanoparticles were studied. The results show high levels of internal doping due to the substitution of Ti{sup 4+} ions by Al{sup 3+} in the TiO{sub 2} lattice. Furthermore, anatase to rutile transformation occurs at higher temperatures when the percentage of doping increases. Therefore, Al doping allows us to control the structural and electronic properties of the nanoparticle synthesized. So, it is possible to obtain nanoparticles with anatase as predominant phase in a higher range of temperature.

  7. Highly Al-doped TiO2 nanoparticles produced by Ball Mill Method: structural and electronic characterization

    International Nuclear Information System (INIS)

    Santos, Desireé M. de los; Navas, Javier; Sánchez-Coronilla, Antonio; Alcántara, Rodrigo; Fernández-Lorenzo, Concha; Martín-Calleja, Joaquín

    2015-01-01

    Highlights: • Highly Al-doped TiO 2 nanoparticles were synthesized using a Ball Mill Method. • Al doping delayed anatase to rutile phase transformation. • Al doping allow controlling the structural and electronic properties of nanoparticles. - Abstract: This study presents an easy method for synthesizing highly doped TiO 2 nanoparticles. The Ball Mill method was used to synthesize pure and Al-doped titanium dioxide, with an atomic percentage up to 15.7 at.% Al/(Al + Ti). The samples were annealed at 773 K, 973 K and 1173 K, and characterized using ICP-AES, XRD, Raman spectroscopy, FT-IR, TG, STEM, XPS, and UV–vis spectroscopy. The effect of doping and the calcination temperature on the structure and properties of the nanoparticles were studied. The results show high levels of internal doping due to the substitution of Ti 4+ ions by Al 3+ in the TiO 2 lattice. Furthermore, anatase to rutile transformation occurs at higher temperatures when the percentage of doping increases. Therefore, Al doping allows us to control the structural and electronic properties of the nanoparticle synthesized. So, it is possible to obtain nanoparticles with anatase as predominant phase in a higher range of temperature

  8. Bioinformatic evidence for a widely distributed, ribosomally produced electron carrier precursor, its maturation proteins, and its nicotinoprotein redox partners

    Directory of Open Access Journals (Sweden)

    Haft Daniel H

    2011-01-01

    Full Text Available Abstract Background Enzymes in the radical SAM (rSAM domain family serve in a wide variety of biological processes, including RNA modification, enzyme activation, bacteriocin core peptide maturation, and cofactor biosynthesis. Evolutionary pressures and relationships to other cellular constituents impose recognizable grammars on each class of rSAM-containing system, shaping patterns in results obtained through various comparative genomics analyses. Results An uncharacterized gene cluster found in many Actinobacteria and sporadically in Firmicutes, Chloroflexi, Deltaproteobacteria, and one Archaeal plasmid contains a PqqE-like rSAM protein family that includes Rv0693 from Mycobacterium tuberculosis. Members occur clustered with a strikingly well-conserved small polypeptide we designate "mycofactocin," similar in size to bacteriocins and PqqA, precursor of pyrroloquinoline quinone (PQQ. Partial Phylogenetic Profiling (PPP based on the distribution of these markers identifies the mycofactocin cluster, but also a second tier of high-scoring proteins. This tier, strikingly, is filled with up to thirty-one members per genome from three variant subfamilies that occur, one each, in three unrelated classes of nicotinoproteins. The pattern suggests these variant enzymes require not only NAD(P, but also the novel gene cluster. Further study was conducted using SIMBAL, a PPP-like tool, to search these nicotinoproteins for subsequences best correlated across multiple genomes to the presence of mycofactocin. For both the short chain dehydrogenase/reductase (SDR and iron-containing dehydrogenase families, aligning SIMBAL's top-scoring sequences to homologous solved crystal structures shows signals centered over NAD(P-binding sites rather than over substrate-binding or active site residues. Previous studies on some of these proteins have revealed a non-exchangeable NAD cofactor, such that enzymatic activity in vitro requires an artificial electron acceptor such

  9. The mechanism for enhanced oxidation degradation of dioxin-like PCBs (PCB-77) in the atmosphere by the solvation effect.

    Science.gov (United States)

    Xin, Mei-Ling; Yang, Jia-Wen; Li, Yu

    2017-07-11

    The reaction pathways of PCB-77 in the atmosphere with ·OH, O 2 , NO x , and 1 O 2 were inferred based on density functional theory calculations with the 6-31G* basis set. The structures the reactants, transition states, intermediates, and products were optimized. The energy barriers and reaction heats were obtained to determine the energetically favorable reaction pathways. To study the solvation effect, the energy barriers and reaction rates for PCB-77 with different polar and nonpolar solvents (cyclohexane, benzene, carbon tetrachloride, chloroform, acetone, dichloromethane, ethanol, methanol, acetonitrile, dimethylsulfoxide, and water) were calculated. The results showed that ·OH preferentially added to the C5 atom of PCB-77, which has no Cl atom substituent, to generate the intermediate IM5. This intermediate subsequently reacted with O 2 via pathway A to generate IM5a, with an energy barrier of 7.27 kcal/mol and total reaction rate of 8.45 × 10 -8  cm 3 /molecule s. Pathway B involved direct dehydrogenation of IM5 to produce the OH-PCBs intermediate IM5b, with an energy barrier of 28.49 kcal/mol and total reaction rate of 1.15 × 10 -5  cm 3 /molecule s. The most likely degradation pathway of PCB-77 in the atmosphere is pathway A to produce IM5a. The solvation effect results showed that cyclohexane, carbon tetrachloride, and benzene could reduce the reaction energy barrier of pathway A. Among these solvents, the solvation effect of benzene was the largest, and could reduce the total reaction energy barrier by 25%. Cyclohexane, carbon tetrachloride, benzene, dichloromethane, acetone, and ethanol could increase the total reaction rate of pathway A. The increase in the reaction rate of pathway A with benzene was 8%. The effect of solvents on oxidative degradation of PCB-77 in the atmosphere is important. Graphical abstract The reaction pathways of PCB-77 in the atmosphere with •OH, O2, NOx, and 1O2 were inferred based on density functional theory

  10. Retrograde amnesia produced by electron beam exposure: casual parameters and duration of memory loss. Final report for November 84

    Energy Technology Data Exchange (ETDEWEB)

    Wheeler, T.G.; Hardy, K.A.

    1985-01-01

    The production of retrograde amnesia (RA) upon electron-beam exposure was investigated. RA production was evaluated using a single-trial avoidance task for 10, 1, and 0.1 microsecond pulsed exposures. The dose-response curve obtained at each pulse duration showed significant RA production. The most effective dose range was 0.1-10 rad at a dose rate of 1,000,000 rad/sec. By employing a 10 rad (1,000,000 rad/s) pulse, a memory loss of the events occurring in the previous 4 sec was demonstrated. The conclusion was that the RA effect might be due to sensory system activation which provided a novel stimulus that masked previous stimuli.

  11. Temporal properties of coherent synchrotron radiation produced by an electron bunch moving along an arc of a circle

    International Nuclear Information System (INIS)

    Geloni, G.; Saldin, E.L.; Schneidmiller, E.A.; Yurkov, M.V.

    2004-01-01

    In the limit for a large distance between bunch and detector and under the assumption that the entire process, i.e. radiation and detection, happens in vacuum, one can use the well-known Schwinger formulas in order to describe the single-particle radiation in the case of circular motion. Nevertheless, these formulas cannot be applied for particles moving in an arc of a circle. In this paper, we present a characterization of coherent synchrotron radiation (CSR) pulses in the time-domain as they are emitted by an electron bunch moving in an arc of a circle. This can be used in order to give a quantitative estimation of the effects of a finite bending magnet extension on the characteristics of the CSR pulse

  12. Evolution of an electron-positron plasma produced by induced gravitational collapse in binary-driven hypernovae

    Directory of Open Access Journals (Sweden)

    Melon Fuksman J. D.

    2018-01-01

    Full Text Available The binary-driven hypernova (BdHN model has been introduced in the past years, to explain a subfamily of gamma-ray bursts (GRBs with energies Eiso ≥ 1052 erg associated with type Ic supernovae. Such BdHNe have as progenitor a tight binary system composed of a carbon-oxigen (CO core and a neutron star undergoing an induced gravitational collapse to a black hole, triggered by the CO core explosion as a supernova (SN. This collapse produces an optically-thick e+e- plasma, which expands and impacts onto the SN ejecta. This process is here considered as a candidate for the production of X-ray flares, which are frequently observed following the prompt emission of GRBs. In this work we follow the evolution of the e+e- plasma as it interacts with the SN ejecta, by solving the equations of relativistic hydrodynamics numerically. Our results are compatible with the Lorentz factors estimated for the sources that produce the flares, of typically Γ ≲ 4.

  13. Hybrid TiO2 Solar Cells Produced from Aerosolized Nanoparticles of Water-Soluble Polythiophene Electron Donor Layer

    Directory of Open Access Journals (Sweden)

    Marshall L. Sweet

    2014-01-01

    Full Text Available Hybrid solar cells (HSCs with water soluble polythiophene sodium poly[2-(3-thienyl-ethyloxy-4-butylsulfonate] (PTEBS thin films produced using electrospray deposition (ESD were fabricated, tested, and modeled and compared to devices produced using conventional spin coating. A single device structure of FTO/TiO2/PTEBS/Au was used to study the effects of ESD of the PTEBS layer on device performance. ESD was found to increase the short circuit current density (Jsc by a factor of 2 while decreasing the open circuit voltage (Voc by half compared to spin coated PTEBS films. Comparable efficiencies of 0.009% were achieved from both device construction types. Current-voltage curves were modeled using the characteristic solar cell equation and showed a similar increase in generated photocurrent with an increase by two orders of magnitude in the saturation current in devices from ESD films. Increases in Jsc are attributed to an increase in the interfacial contact area between the TiO2 and PTEBS layers, while decreases in Voc are attributed to incomplete film formation from ESD.

  14. Molecular modeling of nucleic Acid structure: electrostatics and solvation.

    Science.gov (United States)

    Bergonzo, Christina; Galindo-Murillo, Rodrigo; Cheatham, Thomas E

    2014-12-19

    This unit presents an overview of computer simulation techniques as applied to nucleic acid systems, ranging from simple in vacuo molecular modeling techniques to more complete all-atom molecular dynamics treatments that include an explicit representation of the environment. The third in a series of four units, this unit focuses on critical issues in solvation and the treatment of electrostatics. UNITS 7.5 & 7.8 introduced the modeling of nucleic acid structure at the molecular level. This included a discussion of how to generate an initial model, how to evaluate the utility or reliability of a given model, and ultimately how to manipulate this model to better understand its structure, dynamics, and interactions. Subject to an appropriate representation of the energy, such as a specifically parameterized empirical force field, the techniques of minimization and Monte Carlo simulation, as well as molecular dynamics (MD) methods, were introduced as a way of sampling conformational space for a better understanding of the relevance of a given model. This discussion highlighted the major limitations with modeling in general. When sampling conformational space effectively, difficult issues are encountered, such as multiple minima or conformational sampling problems, and accurately representing the underlying energy of interaction. In order to provide a realistic model of the underlying energetics for nucleic acids in their native environments, it is crucial to include some representation of solvation (by water) and also to properly treat the electrostatic interactions. These subjects are discussed in detail in this unit. Copyright © 2014 John Wiley & Sons, Inc.

  15. Comparison of electron density profiles observed in China's low latitude station with that produced by the International Reference Ionosphere (IRI2001)

    International Nuclear Information System (INIS)

    Zhang Manlian; Shi Jiankui; Wang Xiao

    2003-01-01

    One month's data of ionograms observed by DPS-4 digisonde in China's low latitude station Hainan (19.4 deg N/109.0 deg E) for the high solar activity year 2002 is used to make a comparison study between the observational electron density profiles and that produced by the newly updated International Reference Ionosphere (IRI2001). The present study showed that for the month studied (April, 2002): (1) When B0-Tab value is used, profiles given by IRI2001 are in poor agreement with the observational results during daytime and nearby midnight hours when standard Ne(h) option is chosen, whereas when the LAY functions version is chosen, IRI2001 produces profiles with erroneous features during evening and nighttime hours, although it produces profiles in a reasonable good agreement with the observational ones during daytime hours. (2) In general, profiles produced by IRI2001 with B0-Gulyaeva choice is in better agreement with observational profiles than when B0-Tab is chosen. When the B0-Gulyaeva and LAY functions version of Ne(h) are both chosen, IRI2001 produced the best results when compared with the observational results. (3) The B0 parameter given by B0-Gulyaeva choice in IRI2001 is much closer to the observed (best fitted) one than that given by the B0-Tab choice is. (author)

  16. Effect of electrode for producing the highly charged heavy ions from RIKEN 18 GHz electron cyclotron resonance ion source

    International Nuclear Information System (INIS)

    Kurita, Tetsuro; Nakagawa, Takahide; Kidera, Masanori

    1999-01-01

    We successfully produced the intense beam of highly charged Kr ions using an electrode. Under the pulsed mode operation, we found that the depth of the plasma potential dip strongly depends on the duration of the microwave and takes about 40 ms to reach the equilibrium state. Taking these results into account, we compared the beam intensities of highly charged Kr ions with and without the use of an electrode under the pulsed mode operation. We observed that the density of highly charged Kr ions and ion confinement time increase with increasing mirror magnetic field strength. The plasma potential dip becomes shallower with insertion of the electrode. Consequently, when we increase the mirror magnetic field strength and insert the electrode into the plasma, the beam intensities of highly charged ions increase. (author)

  17. Electronic-state distribution of Ar* produced from Ar+(2P3/2)/2e- collisional radiative recombination in an argon flowing afterglow

    International Nuclear Information System (INIS)

    Tsuji, Masaharu; Matsuzaki, Toshinori; Tsuji, Takeshi

    2002-01-01

    The Ar + /2e - collisional radiative recombination has been studied by observing UV and visible emissions of Ar* in an Ar flowing afterglow. In order to clarify recombination mechanism, the Ar + ( 2 P 3/2 ) spin-orbit component was selected by using a filter gas of the Ar + ( 2 P 1/2 ) component. Spectral analysis indicated that 34 Ar*(4p, 4d, 5p, 5d, 6s, 6p, 6d, 4p ' , 4d ' , 5p ' , 5d ' , 6s ' ) states in the 13.08-15.33 eV range are produced. The electronic-state distribution decreased with an increase in the excitation energy of Ar*, which was expressed by a Boltzmann electronic temperature of 0.54 eV. The formation ratios of the 4p: 4d + 5p + 5d + 6s + 6p + 6d: 4p ' : 4d ' + 5p ' + 5d ' + 6s ' states were 43%, 2.8%, 54%, and 0.31%, respectively. The high formation ratio of the 4p ' state having an Ar + ( 2 P 1/2 ) ion core in the Ar + ( 2 P 3/2 )/2e - recombination indicated that such a two-electron process as an electron transfer to an inner 3p orbital followed by excitation of a 3p electron to an outer 4p orbital occurs significantly. The higher formation ratios of 4d + 5p + 5d + 6s + 6p + 6d than those of 4d ' + 5p ' + 5d ' + 6s ' led us to conclude the formation of these upper states dominantly proceeds through one electron transfer to an outer nl orbital of Ar + ( 2 P 3/2 )

  18. Microstructure and mechanical properties of Al-Fe-V-Si aluminum alloy produced by electron beam melting

    Energy Technology Data Exchange (ETDEWEB)

    Sun, Shaobo; Zheng, Lijing, E-mail: zhenglijing@buaa.edu.cn; Peng, Hui; Zhang, Hu

    2016-04-06

    Atomized, pre-alloyed Al-8.5Fe-1.3V-1.7Si (wt%) powder was used to fabricate solid components by electron beam melting (EBM). The residual porosity, chemical composition, microstructure and mechanical properties have been investigated. Results show that the relative density of as-built alloy under the optimized processing parameters was 98.2%. Compare to the initial alloy powder, the EBM parts demonstrated a restricted aluminum loss (~1 wt%) and a quite low oxygen pickup. The microstructure of the deposits was non-uniform. The fusion zone and heat affected zone exhibited a large number of fine spherical Al{sub 12}(Fe,V){sub 3}Si particles (30–110 nm) distributed uniformly in the α-Al matrix. Some coarser Fe- and V-riched rectangle-like Al{sub m}Fe phase (m=4.0–4.4) with 100–400 nm in size was precipitated in the melting boundary zone. The microhardness of the EBM samples was 153 HV in average. The average ultimate tensile strength (UTS) reached 438 MPa with the elongation of 12%. A ductile fracture mode of the tensile specimens was also revealed.

  19. Hydroxyapatite, fluor-hydroxyapatite and fluorapatite produced via the sol-gel method: bonding to titanium and scanning electron microscopy.

    Science.gov (United States)

    Tredwin, Christopher J; Georgiou, George; Kim, Hae-Won; Knowles, Jonathan C

    2013-05-01

    Hydroxyapatite (HA), fluor-hydroxyapatite (FHA) with varying levels of fluoride ion substitution and fluorapatite (FA) production has been characterised and optimised by the sol-gel method and the dissolution and biological properties of these materials were investigated. It was the objective of this study to investigate the potential bond strength and interaction of these materials with titanium. HA, FHA and FA were synthesised by a sol-gel method. Calcium nitrate and triethyl phosphite were used as precursors under an ethanol-water based solution. Different amounts of ammonium fluoride (NH4F) were incorporated for the preparation of the FHA and FA sol-gels. Using a spin coating technique the sol-gels were coated onto commercially pure titanium disks and crystallised at various temperatures. Using scanning electron microscopy (SEM) and elemental analysis, the surface characteristics, coating thickness and interaction of the Ti substrate and coating were investigated. The bond strengths of the coating to the Ti were investigated using an Instron Universal Load Testing Machine. Statistical analysis was performed with a two-way analysis of variance and post hoc testing with a Bonferroni correction. (1) Coating speed inversely influenced the coating thickness. (2) Increasing fluoride ion substitution and heating temperature significantly increased bond strength and (3) increasing fluoride ion substitution increased the coating thickness. FHA and FA synthesised using the sol-gel technique may offer a superior alternative to coating titanium implants with HA and plasma spraying. HA, FHA and FA materials synthesised by the sol-gel method may also have a use as bone grafting materials. Copyright © 2013 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

  20. Continuum model of non-equilibrium solvation and solvent effect on ultra-fast processes

    International Nuclear Information System (INIS)

    Li Xiangyuan; Fu Kexiang; Zhu Quan

    2006-01-01

    In the past 50 years, non-equilibrium solvation theory for ultra-fast processes such as electron transfer and light absorption/emission has attracted particular interest. A great deal of research efforts was made in this area and various models which give reasonable qualitative descriptions for such as solvent reorganization energy in electron transfer and spectral shift in solution, were developed within the framework of continuous medium theory. In a series of publications by the authors, we clarified that the expression of the non-equilibrium electrostatic free energy that is at the dominant position of non-equilibrium solvation and serves as the basis of various models, however, was incorrectly formulated. In this work, the authors argue that reversible charging work integration was inappropriately applied in the past to an irreversible path linking the equilibrium or the non-equilibrium state. Because the step from the equilibrium state to the nonequilibrium state is factually thermodynamically irreversible, the conventional expression for non-equilibrium free energy that was deduced in different ways is unreasonable. Here the authors derive the non-equilibrium free energy to a quite different form according to Jackson integral formula. Such a difference throws doubts to the models including the famous Marcus two-sphere model for solvent reorganization energy of electron transfer and the Lippert-Mataga equation for spectral shift. By introducing the concept of 'spring energy' arising from medium polarizations, the energy constitution of the non-equilibrium state is highlighted. For a solute-solvent system, the authors separate the total electrostatic energy into different components: the self-energies of solute charge and polarized charge, the interaction energy between them and the 'spring energy' of the solvent polarization. With detailed reasoning and derivation, our formula for non-equilibrium free energy can be reached through different ways. Based on the

  1. Solvation of positive ions in water: the dominant role of water-water interaction

    International Nuclear Information System (INIS)

    Krekeler, Christian; Site, Luigi Delle

    2007-01-01

    Local polarization effects, induced by monovalent and divalent positive ions in water, influence (and in turn are influenced by) the large-scale structural properties of the solvent. Experiments can only distinguish this process of interplay in a generic qualitative way. Instead, first-principles calculations can address the question at both the electronic and atomistic scale, accounting for electronic polarization as well as geometrical conformations. For this reason we study the extension of the scales' interconnection by means of first-principle Car-Parrinello molecular dynamics applied to systems of different size. In this way we identify the general aspects dominating the physics of the first solvation shell and their connection to the effects related to the formation of the outer shells and eventually the bulk. We show that while the influence of the ions is extended to the first shell only, the water-water interaction is instead playing a dominant role even within the first shell independently of the size or the charge of the ion. (fast track communication)

  2. Low-energy x-ray and electron physics and applications to diagnostics development for laser-produced plasma research. Final report, April 30, 1980-April 29, 1981

    Energy Technology Data Exchange (ETDEWEB)

    Henke, B.L.

    1981-08-01

    This final report describes a collaborative extension of an ongoing research program in low-energy x-ray and electron physics into particular areas of immediate need for the diagnostics of plasmas as involved in laser-produced fusion research. It has been for the continued support for one year of a post-doctoral research associate and for three student research assistants who have been applied to the following specific efforts: (1) the continuation of our research on the absolute characterization of x-ray photocathode systems for the 0.1 to 10 keV photon energy region. The research results were applied collaboratively to the design, construction and calibration of photocathodes for time-resolved detection with the XRD and the streak and framing cameras; (2) the design, construction and absolute calibration of optimized, bolt-on spectrographs for the absolute measurement of laser-produced plasma spectra.

  3. Low-energy x-ray and electron physics and applications to diagnostics development for laser-produced plasma research. Final report, April 30, 1980-April 29, 1981

    International Nuclear Information System (INIS)

    Henke, B.L.

    1981-08-01

    This final report describes a collaborative extension of an ongoing research program in low-energy x-ray and electron physics into particular areas of immediate need for the diagnostics of plasmas as involved in laser-produced fusion research. It has been for the continued support for one year of a post-doctoral research associate and for three student research assistants who have been applied to the following specific efforts: (1) the continuation of our research on the absolute characterization of x-ray photocathode systems for the 0.1 to 10 keV photon energy region. The research results were applied collaboratively to the design, construction and calibration of photocathodes for time-resolved detection with the XRD and the streak and framing cameras; (2) the design, construction and absolute calibration of optimized, bolt-on spectrographs for the absolute measurement of laser-produced plasma spectra

  4. Thermo-stable carbon nanotube-TiO_2 nanocompsite as electron highways in dye-sensitized solar cell produced by bio-nano-process

    International Nuclear Information System (INIS)

    Inoue, Ippei; Yasueda, Hisashi; Yamauchi, Hirofumi; Okamoto, Naofumi; Toyoda, Kenichi; Horita, Masahiro; Ishikawa, Yasuaki; Uraoka, Yukiharu; Yamashita, Ichiro

    2015-01-01

    We produced a thermostable TiO_2-(anatase)-coated multi-walled-carbon-nanotube (MWNT) nanocomposite for use in dye-sensitized solar cells (DSSCs) using biological supuramolecules as catalysts. We synthesized two different sizes of iron oxide nanoparticles (NPs) and arrayed the NPs on a silicon substrate utilizing two kinds of genetically modified cage-shaped proteins with silicon-binding peptide aptamers on their outer surfaces. Chemical vapor deposition (CVD) with the vapor–liquid-solid phase (VLS) method was applied to the substrate, and thermostable MWNTs with a diameter of 6 ± 1 nm were produced. Using a genetically modified cage-shaped protein with carbon-nanomaterials binding and Ti-mineralizing peptides as a catalyst, we were able to mineralize a titanium compound around the surface of the MWNT. The products were sintered, and thin TiO_2-layer-coated MWNTs nanocomoposites were successfully produced. Addition of a 0.2 wt% TiO_2-coated MWNT nanocomposite to a DSSC photoelectrode improved current density by 11% and decreased electric resistance by 20% compared to MWNT-free reference DSSCs. These results indicate that a nanoscale TiO_2-layer-coated thermostable MWNT structure produced by our mutant proteins works as a superior electron transfer highway within TiO_2 photoelectrodes. (paper)

  5. Bone ingrowth potential of electron beam and selective laser melting produced trabecular-like implant surfaces with and without a biomimetic coating.

    Science.gov (United States)

    Biemond, J E; Hannink, G; Verdonschot, N; Buma, P

    2013-03-01

    The bone ingrowth potential of trabecular-like implant surfaces produced by either selective laser melting (SLM) or electron beam melting (EBM), with or without a biomimetic calciumphosphate coating, was examined in goats. For histological analysis and histomorphometry of bone ingrowth depth and bone implant contact specimens were implanted in the femoral condyle of goats. For mechanical push out tests to analyse mechanical implant fixation specimens were implanted in the iliac crest. The follow up periods were 4 (7 goats) and 15 weeks (7 goats). Both the SLM and EBM produced trabecular-like structures showed a variable bone ingrowth after 4 weeks. After 15 weeks good bone ingrowth was found in both implant types. Irrespective to the follow up period, and the presence of a coating, no histological differences in tissue reaction around SLM and EBM produced specimens was found. Histological no coating was detected at 4 and 15 weeks follow up. At both follow up periods the mechanical push out strength at the bone implant interface was significantly lower for the coated SLM specimens compared to the uncoated SLM specimens. The expected better ingrowth characteristics and mechanical fixation strength induced by the coating were not found. The lower mechanical strength of the coated specimens produced by SLM is a remarkable result, which might be influenced by the gross morphology of the specimens or the coating characteristics, indicating that further research is necessary.

  6. Selective solvation extraction of gold from alkaline cyanide solution by alkyl phosphorus esters

    Energy Technology Data Exchange (ETDEWEB)

    Miller, J.D.; Wan, R.Y.; Mooiman, M.B.; Sibrell, P.L.

    1987-01-01

    Research efforts have shown that solvation extraction of gold from alkaline cyanide solution is possible by alkyl phosphorus esters. Both tributyl phosphate (TBP) and dibutyl butyl phosphonate (DBBP) appear to be effective extractants for gold and exhibit high loading capacities exceeding 30 gpl. Selective solvation extraction of gold from alkaline cyanide solution can be achieved with selectivity factors relative to other cyanoanions as high as 1000 under certain circumstances. Variables influencing the selectivity such as ionic strength, temperature, and extractant structure, are discussed in terms of the extraction chemistry, which seems to involve the solvation of a M dot, dot, dot Au(CN)2 ion pair.

  7. Solvation of ions in the gas-phase: a molecular dynamics simulation

    Science.gov (United States)

    Cabarcos, Orlando M.; Lisy, James M.

    1996-07-01

    Molecular dynamics simulations have been performed on the collision between a cesium ion and a cluster of twenty methanol molecules. This process, generating a solvated ion, was studied over a range (1 to 25 eV) of eight collision energies. Preliminary analysis of this gas phase solvation has included the distribution of final ion cluster sizes, fragmentation patterns, solvation timescales and energetics. Two distinct patterns have emerged: a ballistic penetration of the neutral cluster at the higher collision energies and an evaporative evolution of the cluster ion at lower collision energies.

  8. Solvation of graphite oxide in water-methanol binary polar solvents

    Energy Technology Data Exchange (ETDEWEB)

    You, Shujie; Yu, Junchun; Sundqvist, Bertil; Talyzin, Alexandr V. [Department of Physics, Umeaa University, SE-901 87 Umeaa (Sweden)

    2012-12-15

    The phase transition between two solvated phases was studied by DSC for graphite oxide (GO) powders immersed in water-methanol mixtures of various compositions. GO forms solid solvates with two different compositions when immersed in methanol. Reversible phase transition between two solvate states due to insertion/desertion of methanol monolayer occurs upon temperature variations. The temperature point and the enthalpy ({Delta}H) of the phase transition are maximal for pure methanol and decrease linearly with increase of water fraction up to 30%. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  9. Selective nonspecific solvation under dielectric saturation and fluorescence spectra of dye solutions in binary solvents.

    Science.gov (United States)

    Bakhshiev, N G; Kiselev, M B

    1991-09-01

    The influence of selective nonspecific solvation on the fluorescence spectra of three substitutedN-methylphthalimides in a binary solvent system consisting of a nonpolar (n-heptane) and a polar (pyridine) component has been studied under conditions close to dielectric saturation. The substantially nonlinearity of the effect is confirmation that the spectral shifts of fluorescence bands depend on the number of polar solvent molecules involved in solvating the dye molecule. The measured fluorescence spectral shifts determined by substituting one nonpolar solvent molecula with a polar one in the proximity of the dye molecule agree quantitatively with the forecasts of the previously proposed semiempirical theory which describes this nonlinear solvation phenomenon.

  10. a Study of Charged d* Mesons Produced in Electron - Annihilation at Center-Of Energy = 29 GEV

    Science.gov (United States)

    Yamamoto, Hitoshi

    Charged D* mesons produced in e('+)e('-) annihilation at a center- of-mass energy of 29 GeV have been studied with the DELCO detec- tor at the PEP storage ring. The selection criteria of D* candidates exploit the (pi)/K separation capability in the momentum range from 2.6 GeV/c to 9.2 GeV/c provided by the gas Cerenkov counter. The data correspond to an integrated luminosity of 147 pb(' -1). We have measured the total production cross section of D*('(+OR-)) to be 0.16 (+OR-) 0.02(statistical) (+OR -) 0.02(systematic) nb x (TBOND) P(,D*)/(E(,beam)('2) - M(,D*)('2))(' 1/2) > 0.35 , and (0.18 (+OR-) 0.02 (+OR -) 0.03) nb (x > 0) if the contribution from bottom quarks is subtracted. The branching fractions used are Br(D*('+) (--->) D('0)(pi)('+)) = 64% and Br(D('0) (--->) K('-)(pi)('+)) = 3%. The systematic errors due to the branching ratios are not included in the errors. With Br(D('0) (--->) K(' -)(pi)('+)) = 4.9%, which is a recent measurement by the MARK III group, the above two cross sections become 0.10 (+OR-) 0.02 (+OR-) 0.02 nb (x > 0.35) and 0.11 (+OR-) 0.02 (+OR-) 0.02 nb (x > 0 and after the sub- traction of the contribution from b quarks). The charm fragmentation function is harder than that for light quarks, and the shape is found to be consistent with the prediction of the string model with a uniform string-breaking probability. Assuming the string model, the string-breaking probability is determined to be (0.019 (+OR-) 0.05 (+OR-) 0.09) GeV/c('2). We have also determined the lifetime of D('0) meson which is detec- ted in the D* decay, with the result. (DIAGRAM, TABLE OR GRAPHIC OMITTED...PLEASE SEE DAI). Together with the semileptonic branching fraction of D('0) measured elsewhere, the semileptonic decay rate of D('0) is estimated to be (1.4 (+OR-) 0.5) x 10('11) sec('-1), which corresponds to an effective charm quark mass of (1.54 (+OR-) 0.12) GeV/c('2). Using part of the D* candidates, we have set an upper limit on D('0)-(')D('0) mixing: r (TBOND) P

  11. Electronics

    Science.gov (United States)

    2001-01-01

    International Acer Incorporated, Hsin Chu, Taiwan Aerospace Industrial Development Corporation, Taichung, Taiwan American Institute of Taiwan, Taipei, Taiwan...Singapore and Malaysia .5 - 4 - The largest market for semiconductor products is the high technology consumer electronics industry that consumes up...Singapore, and Malaysia . A new semiconductor facility costs around $3 billion to build and takes about two years to become operational

  12. Trimesic acid dimethyl sulfoxide solvate: space group revision

    Directory of Open Access Journals (Sweden)

    Sylvain Bernès

    2008-07-01

    Full Text Available The structure of the title solvate, C9H6O6·C2H6OS, was determined 30 years ago [Herbstein, Kapon & Wasserman (1978. Acta Cryst. B34, 1613–1617], with data collected at room temperature, and refined in the space group P21. The present redetermination, based on high-resolution diffraction data, shows that the actual space group is more likely to be P21/m. The crystal structure contains layers of trimesic acid molecules lying on mirror planes. A mirror plane also passes through the S and O atoms of the solvent molecule. The molecules in each layer are interconnected through strong O—H...O hydrogen bonds, forming a two-dimensional supramolecular network within each layer. The donor groups are the hydroxyls of the trimesic acid molecules, while the acceptors are the carbonyl or the sulfoxide O atoms.

  13. Solvation thermodynamics of phenylalcohols in lamellar phase surfactant dispersions

    International Nuclear Information System (INIS)

    Martyniak, A.; Scheuermann, R.; Dilger, H.; Tucker, I.M.; Burkert, T.; Hashmi, A.S.K.; Vujosevic', D.; Roduner, E.

    2006-01-01

    The distribution and the stability of five phenylalcohols in a lamellar phase composed of simple bilayers separated by water at 298 and 348K is explored using avoided-level-crossing muon-spin resonance (ALC-μSR). The dependence of the alignment of the bilayer chains on temperature appears to be a crucial factor determining the phenylalcohol partitioning: increasing order of the surfactant tails leads to expulsion of the solute. Moreover, we observed a systematic trend, the longer the chain the deeper the phenyl group dips into the lipid bilayer. Recent studies have shown that the hydrophobic effect is adequate to describe membrane partitioning of small amphiphilic molecules. The solvation thermodynamic properties ΔG sol , ΔH sol , and ΔS sol which determine the solute transfer from the double layer into water prove that the distribution also strongly depends on shape, chemical nature and different structure of phenylalcohols

  14. Solvation thermodynamics of phenylalcohols in lamellar phase surfactant dispersions

    Energy Technology Data Exchange (ETDEWEB)

    Martyniak, A. [Institut fuer Physikalische Chemie, University of Stuttgart, Pfaffenwaldring 55, D-70569 Stuttgart (Germany); Scheuermann, R. [Laboratory for muon Spin Spectroscopy, Paul Scherrer Institute, CH-5232 Villigen (Switzerland); Dilger, H. [Institut fuer Physikalische Chemie, University of Stuttgart, Pfaffenwaldring 55, D-70569 Stuttgart (Germany); Tucker, I.M. [Unilever Research and Development, Port Sunlight, Wirral CH63 3JW (United Kingdom); Burkert, T. [Institut fuer Organische Chemie, University of Stuttgart, Pfaffenwaldring 55, D-70569 Stuttgart (Germany); Hashmi, A.S.K. [Institut fuer Organische Chemie, University of Stuttgart, Pfaffenwaldring 55, D-70569 Stuttgart (Germany); Vujosevic' , D. [Institut fuer Physikalische Chemie, University of Stuttgart, Pfaffenwaldring 55, D-70569 Stuttgart (Germany); Roduner, E. [Institut fuer Physikalische Chemie, University of Stuttgart, Pfaffenwaldring 55, D-70569 Stuttgart (Germany)]. E-mail: e.roduner@ipc.uni-stuttgart.de

    2006-03-31

    The distribution and the stability of five phenylalcohols in a lamellar phase composed of simple bilayers separated by water at 298 and 348K is explored using avoided-level-crossing muon-spin resonance (ALC-{mu}SR). The dependence of the alignment of the bilayer chains on temperature appears to be a crucial factor determining the phenylalcohol partitioning: increasing order of the surfactant tails leads to expulsion of the solute. Moreover, we observed a systematic trend, the longer the chain the deeper the phenyl group dips into the lipid bilayer. Recent studies have shown that the hydrophobic effect is adequate to describe membrane partitioning of small amphiphilic molecules. The solvation thermodynamic properties {delta}G{sub sol}, {delta}H{sub sol}, and {delta}S{sub sol} which determine the solute transfer from the double layer into water prove that the distribution also strongly depends on shape, chemical nature and different structure of phenylalcohols.

  15. Formation of (Xe2H)* centers in solid Xe via recombination: nonstationary luminescence and 'internal electron emission'

    International Nuclear Information System (INIS)

    Savchenko, E.V.; Khyzhniy, I.V.; Uyutov, S.A.; Gumenchuk, G.B.; Ponomarev, A.N.; Bondybey, V.E.; Beyer, M.K.

    2010-01-01

    The formation of excimers (Xe 2 H) * in solid Xe doped with molecular hydrogen under electron beam is studied using the original two-stage technique of nonstationary (NS) cathodoluminescence (CL) in combination with the current activation spectroscopy method - thermally stimulated exoelectron emission (TSEE). Charged species were generated using a high-density electron beam. The species produced were then probed with a low density beam on gradual sample heating. The near UV emission of the (Xe 2 H) * was used to monitor the neutralization process. It is found that the temperature behavior of the NS CL band of (Xe 2 H) * clearly correlates with the yield of TSEE measured after identical pre-irradiation of the sample. The fingerprints of the thermally stimulated detrapping of electrons - 'internal electron emission' in the spectrum of NS CL point to the essential role of neutralization reaction in the stability of the proton solvated by rare-gas atoms.

  16. MTS-MD of Biomolecules Steered with 3D-RISM-KH Mean Solvation Forces Accelerated with Generalized Solvation Force Extrapolation.

    Science.gov (United States)

    Omelyan, Igor; Kovalenko, Andriy

    2015-04-14

    We developed a generalized solvation force extrapolation (GSFE) approach to speed up multiple time step molecular dynamics (MTS-MD) of biomolecules steered with mean solvation forces obtained from the 3D-RISM-KH molecular theory of solvation (three-dimensional reference interaction site model with the Kovalenko-Hirata closure). GSFE is based on a set of techniques including the non-Eckart-like transformation of coordinate space separately for each solute atom, extension of the force-coordinate pair basis set followed by selection of the best subset, balancing the normal equations by modified least-squares minimization of deviations, and incremental increase of outer time step in motion integration. Mean solvation forces acting on the biomolecule atoms in conformations at successive inner time steps are extrapolated using a relatively small number of best (closest) solute atomic coordinates and corresponding mean solvation forces obtained at previous outer time steps by converging the 3D-RISM-KH integral equations. The MTS-MD evolution steered with GSFE of 3D-RISM-KH mean solvation forces is efficiently stabilized with our optimized isokinetic Nosé-Hoover chain (OIN) thermostat. We validated the hybrid MTS-MD/OIN/GSFE/3D-RISM-KH integrator on solvated organic and biomolecules of different stiffness and complexity: asphaltene dimer in toluene solvent, hydrated alanine dipeptide, miniprotein 1L2Y, and protein G. The GSFE accuracy and the OIN efficiency allowed us to enlarge outer time steps up to huge values of 1-4 ps while accurately reproducing conformational properties. Quasidynamics steered with 3D-RISM-KH mean solvation forces achieves time scale compression of conformational changes coupled with solvent exchange, resulting in further significant acceleration of protein conformational sampling with respect to real time dynamics. Overall, this provided a 50- to 1000-fold effective speedup of conformational sampling for these systems, compared to conventional MD

  17. A new apparatus for the study of electron impact fragmentation of molecular clusters

    International Nuclear Information System (INIS)

    Barrett, G; Burgt, P J M van der

    2008-01-01

    This paper reports on the development of a new experiment for the study of electron-impact induced dissociation and fragmentation of molecular clusters and biomolecules and other species solvated in water clusters. The purpose is to look at clusters that are of interest to biophysics, atmospheric physics, and other fields. The experiment consists of a differentially pumped vacuum system, with an expansion chamber to generate a pulsed supersonic beam of clusters, and a collision chamber where the cluster beam intersects with an electron beam. Water clusters can be seeded with biomolecules emerging from a resistively heated oven. Investigation will be possible into both ion yields and long-lived neutral metastable yields produced by electron-impact fragmentation of relevant clusters and biomolecules

  18. Theory of competitive solvation of polymers by two solvents and entropy-enthalpy compensation in the solvation free energy upon dilution with the second solvent.

    Science.gov (United States)

    Dudowicz, Jacek; Freed, Karl F; Douglas, Jack F

    2015-06-07

    We develop a statistical mechanical lattice theory for polymer solvation by a pair of relatively low molar mass solvents that compete for binding to the polymer backbone. A theory for the equilibrium mixture of solvated polymer clusters {AiBCj} and free unassociated molecules A, B, and C is formulated in the spirit of Flory-Huggins mean-field approximation. This theoretical framework enables us to derive expressions for the boundaries for phase stability (spinodals) and other basic properties of these polymer solutions: the internal energy U, entropy S, specific heat CV, extent of solvation Φsolv, average degree of solvation 〈Nsolv〉, and second osmotic virial coefficient B2 as functions of temperature and the composition of the mixture. Our theory predicts many new phenomena, but the current paper applies the theory to describe the entropy-enthalpy compensation in the free energy of polymer solvation, a phenomenon observed for many years without theoretical explanation and with significant relevance to liquid chromatography and other polymer separation methods.

  19. Comparative Analysis of the Oxygen Supply and Viability of Human Osteoblasts in Three-Dimensional Titanium Scaffolds Produced by Laser-Beam or Electron-Beam Melting

    Directory of Open Access Journals (Sweden)

    Anika Jonitz-Heincke

    2013-11-01

    Full Text Available Synthetic materials for bone replacement must ensure a sufficient mechanical stability and an adequate cell proliferation within the structures. Hereby, titanium materials are suitable for producing patient-individual porous bone scaffolds by using generative techniques. In this in vitro study, the viability of human osteoblasts was investigated in porous 3D Ti6Al4V scaffolds, which were produced by electron-beam (EBM or laser-beam melting (LBM. For each examination, two cylindrical scaffolds (30 mm × 10 mm in size, 700 µm × 700 µm macropores were placed on each other and seeded with cells. The oxygen consumption and the acidification in the center of the structures were investigated by means of microsensors. Additionally, the synthesis of pro-collagen type 1 was analyzed. On the LBM titanium scaffolds, vital bone cells were detected in the center and in the periphery after 8 days of cultivation. In the EBM titanium constructs, however, vital cells were only visible in the center. During the cultivation period, the cells increasingly produced procollagen type 1 in both scaffolds. In comparison to the periphery, the oxygen content in the center of the scaffolds slightly decreased. Furthermore, a slight acidification of the medium was detectable. Compared to LBM, the EBM titanium scaffolds showed a less favorable behavior with regard to cell seeding.

  20. Electron Tunneling in Lithium Ammonia Solutions Probed by Frequency-Dependent Electron-Spin Relaxation Studies

    Science.gov (United States)

    Maeda, Kiminori; Lodge, Matthew T.J.; Harmer, Jeffrey; Freed, Jack H.; Edwards, Peter P.

    2012-01-01

    Electron transfer or quantum tunneling dynamics for excess or solvated electrons in dilute lithium-ammonia solutions have been studied by pulse electron paramagnetic resonance (EPR) spectroscopy at both X- (9.7 GHz) and W-band (94 GHz) frequencies. The electron spin-lattice (T1) and spin-spin (T2) relaxation data indicate an extremely fast transfer or quantum tunneling rate of the solvated electron in these solutions which serves to modulate the hyperfine (Fermi-contact) interaction with nitrogen nuclei in the solvation shells of ammonia molecules surrounding the localized, solvated electron. The donor and acceptor states of the solvated electron in these solutions are the initial and final electron solvation sites found before, and after, the transfer or tunneling process. To interpret and model our electron spin relaxation data from the two observation EPR frequencies requires a consideration of a multi-exponential correlation function. The electron transfer or tunneling process that we monitor through the correlation time of the nitrogen Fermi-contact interaction has a time scale of (1–10)×10−12 s over a temperature range 230–290K in our most dilute solution of lithium in ammonia. Two types of electron-solvent interaction mechanisms are proposed to account for our experimental findings. The dominant electron spin relaxation mechanism results from an electron tunneling process characterized by a variable donor-acceptor distance or range (consistent with such a rapidly fluctuating liquid structure) in which the solvent shell that ultimately accepts the transferring electron is formed from random, thermal fluctuations of the liquid structure in, and around, a natural hole or Bjerrum-like defect vacancy in the liquid. Following transfer and capture of the tunneling electron, further solvent-cage relaxation with a timescale of ca. 10−13 s results in a minor contribution to the electron spin relaxation times. This investigation illustrates the great potential

  1. Electron tunneling in lithium-ammonia solutions probed by frequency-dependent electron spin relaxation studies.

    Science.gov (United States)

    Maeda, Kiminori; Lodge, Matthew T J; Harmer, Jeffrey; Freed, Jack H; Edwards, Peter P

    2012-06-06

    Electron transfer or quantum tunneling dynamics for excess or solvated electrons in dilute lithium-ammonia solutions have been studied by pulse electron paramagnetic resonance (EPR) spectroscopy at both X- (9.7 GHz) and W-band (94 GHz) frequencies. The electron spin-lattice (T(1)) and spin-spin (T(2)) relaxation data indicate an extremely fast transfer or quantum tunneling rate of the solvated electron in these solutions which serves to modulate the hyperfine (Fermi-contact) interaction with nitrogen nuclei in the solvation shells of ammonia molecules surrounding the localized, solvated electron. The donor and acceptor states of the solvated electron in these solutions are the initial and final electron solvation sites found before, and after, the transfer or tunneling process. To interpret and model our electron spin relaxation data from the two observation EPR frequencies requires a consideration of a multiexponential correlation function. The electron transfer or tunneling process that we monitor through the correlation time of the nitrogen Fermi-contact interaction has a time scale of (1-10) × 10(-12) s over a temperature range 230-290 K in our most dilute solution of lithium in ammonia. Two types of electron-solvent interaction mechanisms are proposed to account for our experimental findings. The dominant electron spin relaxation mechanism results from an electron tunneling process characterized by a variable donor-acceptor distance or range (consistent with such a rapidly fluctuating liquid structure) in which the solvent shell that ultimately accepts the transferring electron is formed from random, thermal fluctuations of the liquid structure in, and around, a natural hole or Bjerrum-like defect vacancy in the liquid. Following transfer and capture of the tunneling electron, further solvent-cage relaxation with a time scale of ∼10(-13) s results in a minor contribution to the electron spin relaxation times. This investigation illustrates the great

  2. Electrical resistivities and solvation enthalpies for solutions of salts in liquid alkali metals

    International Nuclear Information System (INIS)

    Hubberstey, P.; Dadd, A.T.

    1982-01-01

    An empirical correlation is shown to exist between the resistivity coefficients drho/dc for solutes in liquid alkali metals and the corresponding solvation enthalpies Usub(solvn) of the neutral gaseous solute species. Qualitative arguments based on an electrostatic solvation model in which the negative solute atom is surrounded by a solvation sphere of positive solvent ion cores are used to show that both parameters are dependent on the charge density of the solute atom and hence on the extent of charge transfer from solvent to solute. Thus as the charge density of the solute increases, the solvation enthalpy increases regularly and the resistivity coefficients pass through a maximum to give the observed approximately parabolic drho/dc versus Usub(solvn) relationship. (Auth.)

  3. Entropic solvation force between surfaces modified by grafted chains: a density functional approach

    Directory of Open Access Journals (Sweden)

    O. Pizio

    2010-01-01

    Full Text Available The behavior of a hard sphere fluid in slit-like pores with walls modified by grafted chain molecules composed of hard sphere segments is studied using density functional theory. The chains are grafted to opposite walls via terminating segments forming pillars. The effects of confinement and of "chemical" modification of pore walls on the entropic solvation force are investigated in detail. We observe that in the absence of adsorbed fluid the solvation force is strongly repulsive for narrow pores and attractive for wide pores. In the presence of adsorbed fluid both parts of the curve of the solvation force may develop oscillatory behavior dependent on the density of pillars, the number of segments and adsorption conditions. Also, the size ratio between adsorbed fluid species and chain segments is of importance for the development of oscillations. The choice of these parameters is crucial for efficient manipulation of the solvation force as desired for pores of different width.

  4. Coincident detection of electrons ejected at large angles and target recoil ions produced in multiply ionizing collisions for the 1-MeV/u Oq++Ar collision system

    International Nuclear Information System (INIS)

    Gaither III, C.C.; Breinig, M.; Berryman, J.W.; Hasson, B.F.; Richards, J.D.; Price, K.

    1993-01-01

    The angular distributions of energetic electrons ejected at angles between 45 degree and 135 degree with respect to the incident-beam direction have been measured in coincidence with the charge states of the target recoil ions produced in multiply ionizing collisions for the 1-MeV/u O q+ (q=4,7)+Ar collision systems. These measurements have been made for ∼179-, ∼345-, and ∼505-eV electrons. Additionally, the energy distributions of electrons ejected into specific angular regions have been measured. Ar LMM satellite Auger electrons appear as a peak in the energy spectrum of electrons ejected at all large angles. The center of this peak is found at an electron energy of ∼179 eV. Electrons with ∼179 eV energy, ejected at large angles, are preferentially produced in coincidence with recoil ions of charge state 4+. Electrons with ∼345 eV energy and ∼505 eV energy ejected at large angles are preferentially produced in coincidence with recoil ions of charge state 3+. The angular distributions for these electrons are strongly peaked in the forward direction; essentially no electrons are observed at angles larger than 90 degree. These results are consistent with the dominant production mechanism for energetic electrons ejected at large angles being a binary-encounter process. Differential cross sections have been calculated from these angular distributions. They are on the order of 10 -21 cm 2 /(eV sr)

  5. Solvation thermodynamics and heat capacity of polar and charged solutes in water

    Science.gov (United States)

    Sedlmeier, Felix; Netz, Roland R.

    2013-03-01

    The solvation thermodynamics and in particular the solvation heat capacity of polar and charged solutes in water is studied using atomistic molecular dynamics simulations. As ionic solutes we consider a F- and a Na+ ion, as an example for a polar molecule with vanishing net charge we take a SPC/E water molecule. The partial charges of all three solutes are varied in a wide range by a scaling factor. Using a recently introduced method for the accurate determination of the solvation free energy of polar solutes, we determine the free energy, entropy, enthalpy, and heat capacity of the three different solutes as a function of temperature and partial solute charge. We find that the sum of the solvation heat capacities of the Na+ and F- ions is negative, in agreement with experimental observations, but our results uncover a pronounced difference in the heat capacity between positively and negatively charged groups. While the solvation heat capacity ΔCp stays positive and even increases slightly upon charging the Na+ ion, it decreases upon charging the F- ion and becomes negative beyond an ion charge of q = -0.3e. On the other hand, the heat capacity of the overall charge-neutral polar solute derived from a SPC/E water molecule is positive for all charge scaling factors considered by us. This means that the heat capacity of a wide class of polar solutes with vanishing net charge is positive. The common ascription of negative heat capacities to polar chemical groups might arise from the neglect of non-additive interaction effects between polar and apolar groups. The reason behind this non-additivity is suggested to be related to the second solvation shell that significantly affects the solvation thermodynamics and due to its large spatial extent induces quite long-ranged interactions between solvated molecular parts and groups.

  6. Role of Dispersive Fluorous Interaction in the Solvation Dynamics of the Perfluoro Group Containing Molecules.

    Science.gov (United States)

    Mondal, Saptarsi; Chaterjee, Soumit; Halder, Ritaban; Jana, Biman; Singh, Prashant Chandra

    2017-08-17

    Perfluoro group containing molecules possess an important self-aggregation property through the fluorous (F···F) interaction which makes them useful for diverse applications such as medicinal chemistry, separation techniques, polymer technology, and biology. In this article, we have investigated the solvation dynamics of coumarin-153 (C153) and coumarin-6H (C6H) in ethanol (ETH), 2-fluoroethanol (MFE), and 2,2,2-trifluoroethanol (TFE) using the femtosecond upconversion technique and molecular dynamics (MD) simulation to understand the role of fluorous interaction between the solute and solvent molecules in the solvation dynamics of perfluoro group containing molecules. The femtosecond upconversion data show that the time scales of solvation dynamics of C6H in ETH, MFE, and TFE are approximately the same whereas the solvation dynamics of C153 in TFE is slow as compared to that of ETH and MFE. It has also been observed that the time scale of solvation dynamics of C6H in ETH and MFE is higher than that of C153 in the same solvents. MD simulation results show a qualitative agreement with the experimental data in terms of the time scale of the slow components of the solvation for all the systems. The experimental and simulation studies combined lead to the conclusion that the solvation dynamics of C6H in all solvents as well as C153 in ETH and MFE is mostly governed by the charge distribution of ester moieties (C═O and O) of dye molecules whereas the solvation of C153 in TFE is predominantly due to the dispersive fluorous interaction (F···F) between the perfluoro groups of the C153 and solvent molecules.

  7. Radiation-induced electron migration in nucleic acids

    International Nuclear Information System (INIS)

    Fuciarelli, A.F.; Sisk, E.C.; Miller, J.H.; Zimbrick, J.D.

    1994-01-01

    Radiation-induced electron migration along DNA is a mechanism by which randomly produced stochastic energy deposition events can lead to non-random types of damage along DNA manifested distal to the sites of the initial energy deposition. Radiation-induced electron migration in nucleic acids has been examined using oligonucleotides containing 5-bromouracil (5-BrU). Interaction of 5-BrU with solvated electrons results in release of bromide ions and formation of uracil-5-yl radicals. Monitoring either bromide ion release or uracil formation provides an opportunity to study electron migration processes in model nucleic acid systems. Using this approach we have discovered that electron migration along oligonucleotides is significantly influenced by the base sequence and strandedness. Migration along 7 base pairs in oligonucleotides containing guanine bases was observed for oligonucleotides irradiated in solution, which compares with mean migration distances of 6-10 bp for Escherichia coli DNA irradiated in solution and 5.5 bp for E. coli DNA irradiated in cells. Evidence also suggests that electron migration can occur preferentially in the 5' to 3' direction along a double-stranded oligonucleotide containing a region of purine bases adjacent to the 5-BrU moiety. Our continued efforts will provide information regarding the contribution of electron transfer along DNA to formation of locally multiply damaged sites created in DNA by exposure to ionizing radiation. (Author)

  8. Producing nano-grained and Al-enriched surface microstructure on AZ91 magnesium alloy by high current pulsed electron beam treatment

    Energy Technology Data Exchange (ETDEWEB)

    Hao, Shengzhi, E-mail: ebeam@dlut.edu.cn; Li, Mincai

    2016-05-15

    Highlights: • HCPEB surface treatment was conducted on AZ91 magnesium alloy. • Surface modified microstructure and phase composition were characterized. • Preferential evaporation of Mg and dissolution of Mg{sub 17}Al{sub 12} phase occurred. • Nano-grained and Al-enriched surface layer was produced of depth ∼8 μm. • Surface microhardness and corrosion resistance were improved simultaneously. - Abstract: Surface treatment of AZ91 magnesium alloy was carried out by high current pulsed electron beam (HCPEB) with accelerating voltage 27 kV and energy density 3 J/cm{sup 2}. The surface microstructure and phase composition were characterized by using optical microscope (OM), X-ray diffraction (XRD), and scanning electron microscope (SEM) equipped with energy dispersive spectrometer (EDS). The surface microhardness and corrosion resistance were measured. Under HCPEB treatments, the preferential evaporation of Mg element occurred intensively on irradiated surface and the initial large Mg{sub 17}Al{sub 12} phases were dissolved. The nano-grained and Al-enriched surface modified layer was ultimately formed of depth ∼8 μm. According to the testing results, the surface microhardness increased from 63 to 141 HK after 30 pulses of HCPEB treatment, while the best improvement of corrosion resistance was obtained by 15 pulses of HCPEB treatment with a cathodic current density decreased by two orders of magnitude as compared with the initial AZ91 sample.

  9. Measurements of electron density and temperature profiles in plasma produced by Nike KrF laser for laser plasma instability research

    Science.gov (United States)

    Oh, Jaechul; Weaver, J. L.; Karasik, M.; Chan, L. Y.

    2015-08-01

    A grid image refractometer (GIR) has been implemented at the Nike krypton fluoride laser facility of the Naval Research Laboratory. This instrument simultaneously measures propagation angles and transmissions of UV probe rays (λ = 263 nm, Δt = 10 ps) refracted through plasma. We report results of the first Nike-GIR measurement on a CH plasma produced by the Nike laser pulse (˜1 ns FWHM) with the intensity of 1.1 × 1015 W/cm2. The measured angles and transmissions were processed to construct spatial profiles of electron density (ne) and temperature (Te) in the underdense coronal region of the plasma. Using an inversion algorithm developed for the strongly refracted rays, the deployed GIR system probed electron densities up to 4 × 1021 cm-3 with the density scale length of 120 μm along the plasma symmetry axis. The resulting ne and Te profiles are verified to be self-consistent with the measured quantities of the refracted probe light.

  10. A novel nuclear pyrometry for the characterization of high-energy bremsstrahlung and electrons produced in relativistic laser-plasma interactions

    International Nuclear Information System (INIS)

    Guenther, M. M.; Sonnabend, K.; Harres, K.; Roth, M.; Brambrink, E.; Vogt, K.; Bagnoud, V.

    2011-01-01

    We present a novel nuclear activation-based method for the investigation of high-energy bremsstrahlung produced by electrons above 7 MeV generated by a high-power laser. The main component is a novel high-density activation target that is a pseudo alloy of several selected isotopes with different photo-disintegration reaction thresholds. The gamma spectrum emitted by the activated targets is used for the reconstruction of the bremsstrahlung spectrum using an analysis method based on Penfold and Leiss. This nuclear activation-based technique allows for the determination of the number of bremsstrahlung photons per energy bin in a wide range energy without any anticipated fit procedures. Furthermore, the analysis method also allows for the determination of the absolute yield, the energy distribution, and the temperature of high-energy electrons at the relativistic laser-plasma interaction region. The pyrometry is sensitive to energies above 7 MeV only, i.e., this diagnostic is insensitive to any low-energy processes.

  11. A novel nuclear pyrometry for the characterization of high-energy bremsstrahlung and electrons produced in relativistic laser-plasma interactions

    Energy Technology Data Exchange (ETDEWEB)

    Guenther, M. M.; Sonnabend, K.; Harres, K.; Roth, M. [Institut fuer Kernphysik, Schlossgartenstr. 9, Technische Universitaet Darmstadt, D-64289 Darmstadt (Germany); Brambrink, E. [Laboratoire pour l' Utilisation des Lasers Intenses, UMR 7605 CNRS-CEA-Ecole Polytechnique-Universite Paris VI, F-91128 Palaiseau (France); Vogt, K.; Bagnoud, V. [GSI - Helmholtzzentrum fuer Schwerionenforschung GmbH, Planckstr. 1, D-64291 Darmstadt (Germany)

    2011-08-15

    We present a novel nuclear activation-based method for the investigation of high-energy bremsstrahlung produced by electrons above 7 MeV generated by a high-power laser. The main component is a novel high-density activation target that is a pseudo alloy of several selected isotopes with different photo-disintegration reaction thresholds. The gamma spectrum emitted by the activated targets is used for the reconstruction of the bremsstrahlung spectrum using an analysis method based on Penfold and Leiss. This nuclear activation-based technique allows for the determination of the number of bremsstrahlung photons per energy bin in a wide range energy without any anticipated fit procedures. Furthermore, the analysis method also allows for the determination of the absolute yield, the energy distribution, and the temperature of high-energy electrons at the relativistic laser-plasma interaction region. The pyrometry is sensitive to energies above 7 MeV only, i.e., this diagnostic is insensitive to any low-energy processes.

  12. Coherent harmonics of a Free Electron Laser obtained by the injection of harmonics produced in gas on the SCSS prototype accelerator

    International Nuclear Information System (INIS)

    Lambert, G.

    2008-02-01

    Today, single-pass Free Electron Lasers (FELs) allow the structure of matter to be studied in the femtosecond domain. Yet, even if the produced radiation, the so-called Self Amplified Spontaneous Emission (SASE) is highly bright, the longitudinal coherence is partial; the spectral and temporal profiles are composed of a series of peaks, called 'spikes', and present important statistical fluctuations. We demonstrate here the strong and coherent amplification of the 5. harmonic of a Ti: Sa laser (800 nm, 10 Hz, 100 fs) generated in a gas cell, i.e. 160 nm, and seeded in a FEL. This spectacular phenomenon is associated to the generation of intense and coherent Non Linear Harmonics (NLH) at 54 nm and 32 nm. The experiment has been carried out on the SCSS (SPring-8 Compact SASE Source, Japan) Prototype Accelerator. This facility is mainly based on a thermionic cathode electron gun, a LINAC and an in-vacuum undulator (2 sections of 4.5 m length), in which the external harmonic source is overlapped transversally, spectrally and temporally with the electron beam (150 MeV, 10 Hz, 1 ps). With only one undulator section, the 160 nm seeded emission achieves three orders of magnitude higher intensity than the un-seeded one, and presents a quasi perfect Gaussian shape in the spectral distribution. Moreover, the FEL saturation length is twice smaller. In view of the low seed level required, such amplification associated to NLH schemes would allow the generation of fully coherent soft X-ray radiations down to the 'water window'. (author)

  13. Internal energy effects on the solvation and reactivity of multiply charged biomolecules for electrospray ionization mass spectroscopy. [Bovine ubiquitin

    Energy Technology Data Exchange (ETDEWEB)

    Light-Wahl, K.J.; Winger, B.E.; Rockwood, A.L.; Smith, R.D.

    1992-06-01

    Mild (capillary) interface conditions which do not completely desolvate the ions of proteins in electrospray ionization mass spectrometry (ESI-MS) may be required to probe the higher order structures and weak associations. For the small protein bovine ubiquitin, two ion distributions (unsolvated ions and unresolved solvated ions) were observed. The resolvable solvation for leucine-enkephalin with methanol and water shows that the use of countercurrent N{sub 2} flow at the capillary affects the solvation observed. 2 figs. (DLC)

  14. The electron as a chemical entity 201 Farday lecture

    International Nuclear Information System (INIS)

    Dainton, F.S.

    1975-01-01

    After an introductory section, the subject is covered in sections, as follows: on 'dropping' an electron into a liquid or an amorphous solid; the preparation of solvated and trapped electrons in condensed media; the physical properties of solvated or trapped electrons (the E.S.R. spectrum and cavity structure; the equivalent conductance, mobility, diffusion constant, and Stokes radius of esub(s)sup(-); the ionic atmosphere relaxation time; the thermodynamic properties of esub(s)sup(-)); spectroscopic and other evidence concerning the cavities (the effects of pressure and temperature on the spectrum; direct evidence for a range of trap sizes for esub(t)sup(-)); the trapping and solvation mechanism; the chemical reactions of esub(s)sup(-); some applications of our knowledge of esub(s)sup(-). (U.K.)

  15. SIRAH: a structurally unbiased coarse-grained force field for proteins with aqueous solvation and long-range electrostatics.

    Science.gov (United States)

    Darré, Leonardo; Machado, Matías Rodrigo; Brandner, Astrid Febe; González, Humberto Carlos; Ferreira, Sebastián; Pantano, Sergio

    2015-02-10

    Modeling of macromolecular structures and interactions represents an important challenge for computational biology, involving different time and length scales. However, this task can be facilitated through the use of coarse-grained (CG) models, which reduce the number of degrees of freedom and allow efficient exploration of complex conformational spaces. This article presents a new CG protein model named SIRAH, developed to work with explicit solvent and to capture sequence, temperature, and ionic strength effects in a topologically unbiased manner. SIRAH is implemented in GROMACS, and interactions are calculated using a standard pairwise Hamiltonian for classical molecular dynamics simulations. We present a set of simulations that test the capability of SIRAH to produce a qualitatively correct solvation on different amino acids, hydrophilic/hydrophobic interactions, and long-range electrostatic recognition leading to spontaneous association of unstructured peptides and stable structures of single polypeptides and protein-protein complexes.

  16. Nonequilibrium quantum solvation with a time-dependent Onsager cavity

    Science.gov (United States)

    Kirchberg, H.; Nalbach, P.; Thorwart, M.

    2018-04-01

    We formulate a theory of nonequilibrium quantum solvation in which parameters of the solvent are explicitly depending on time. We assume in a simplest approach a spherical molecular Onsager cavity with a time-dependent radius. We analyze the relaxation properties of a test molecular point dipole in a dielectric solvent and consider two cases: (i) a shrinking Onsager sphere and (ii) a breathing Onsager sphere. Due to the time-dependent solvent, the frequency-dependent response function of the dipole becomes time-dependent. For a shrinking Onsager sphere, the dipole relaxation is in general enhanced. This is reflected in a temporally increasing linewidth of the absorptive part of the response. Furthermore, the effective frequency-dependent response function shows two peaks in the absorptive part which are symmetrically shifted around the eigenfrequency. By contrast, a breathing sphere reduces damping as compared to the static sphere. Interestingly, we find a non-monotonous dependence of the relaxation rate on the breathing rate and a resonant suppression of damping when both rates are comparable. Moreover, the linewidth of the absorptive part of the response function is strongly reduced for times when the breathing sphere reaches its maximal extension.

  17. Cluster Formation of Polyphilic Molecules Solvated in a DPPC Bilayer

    Directory of Open Access Journals (Sweden)

    Xiang-Yang Guo

    2017-10-01

    Full Text Available We analyse the initial stages of cluster formation of polyphilic additive molecules which are solvated in a dipalmitoylphosphatidylcholine (DPPC lipid bilayer. Our polyphilic molecules comprise an aromatic (trans-bilayer core domain with (out-of-bilayer glycerol terminations, complemented with a fluorophilic and an alkyl side chain, both of which are confined within the aliphatic segment of the bilayer. Large-scale molecular dynamics simulations (1 μ s total duration of a set of six of such polyphilic additives reveal the initial steps towards supramolecular aggregation induced by the specific philicity properties of the molecules. For our intermediate system size of six polyphiles, the transient but recurrent formation of a trimer is observed on a characteristic timescale of about 100 ns. The alkane/perfluoroalkane side chains show a very distinct conformational distribution inside the bilayer thanks to their different philicity, despite their identical anchoring in the trans-bilayer segment of the polyphile. The diffusive mobility of the polyphilic additives is about the same as that of the surrounding lipids, although it crosses both bilayer leaflets and tends to self-associate.

  18. Ionic strength independence of charge distributions in solvation of biomolecules

    Energy Technology Data Exchange (ETDEWEB)

    Virtanen, J. J. [Department of Chemistry, University of Chicago, Chicago, Illinois 60637 (United States); James Franck Institute, University of Chicago, Chicago, Illinois 60637 (United States); Sosnick, T. R. [Department of Biochemistry and Molecular Biology, Institute for Biophysical Dynamics, University of Chicago, Chicago, Illinois 60637 (United States); Computation Institute, University of Chicago, Chicago, Illinois 60637 (United States); Freed, K. F. [Department of Chemistry, University of Chicago, Chicago, Illinois 60637 (United States); James Franck Institute, University of Chicago, Chicago, Illinois 60637 (United States); Computation Institute, University of Chicago, Chicago, Illinois 60637 (United States)

    2014-12-14

    Electrostatic forces enormously impact the structure, interactions, and function of biomolecules. We perform all-atom molecular dynamics simulations for 5 proteins and 5 RNAs to determine the dependence on ionic strength of the ion and water charge distributions surrounding the biomolecules, as well as the contributions of ions to the electrostatic free energy of interaction between the biomolecule and the surrounding salt solution (for a total of 40 different biomolecule/solvent combinations). Although water provides the dominant contribution to the charge density distribution and to the electrostatic potential even in 1M NaCl solutions, the contributions of water molecules and of ions to the total electrostatic interaction free energy with the solvated biomolecule are comparable. The electrostatic biomolecule/solvent interaction energies and the total charge distribution exhibit a remarkable insensitivity to salt concentrations over a huge range of salt concentrations (20 mM to 1M NaCl). The electrostatic potentials near the biomolecule's surface obtained from the MD simulations differ markedly, as expected, from the potentials predicted by continuum dielectric models, even though the total electrostatic interaction free energies are within 11% of each other.

  19. Ionic strength independence of charge distributions in solvation of biomolecules

    International Nuclear Information System (INIS)

    Virtanen, J. J.; Sosnick, T. R.; Freed, K. F.

    2014-01-01

    Electrostatic forces enormously impact the structure, interactions, and function of biomolecules. We perform all-atom molecular dynamics simulations for 5 proteins and 5 RNAs to determine the dependence on ionic strength of the ion and water charge distributions surrounding the biomolecules, as well as the contributions of ions to the electrostatic free energy of interaction between the biomolecule and the surrounding salt solution (for a total of 40 different biomolecule/solvent combinations). Although water provides the dominant contribution to the charge density distribution and to the electrostatic potential even in 1M NaCl solutions, the contributions of water molecules and of ions to the total electrostatic interaction free energy with the solvated biomolecule are comparable. The electrostatic biomolecule/solvent interaction energies and the total charge distribution exhibit a remarkable insensitivity to salt concentrations over a huge range of salt concentrations (20 mM to 1M NaCl). The electrostatic potentials near the biomolecule's surface obtained from the MD simulations differ markedly, as expected, from the potentials predicted by continuum dielectric models, even though the total electrostatic interaction free energies are within 11% of each other

  20. Preferential solvation and solvation shell composition of free base and protonated 5, 10, 15, 20-tetrakis(4-sulfonatophenyl)porphyrin in aqueous organic mixed solvents

    Science.gov (United States)

    Farajtabar, Ali; Jaberi, Fatemeh; Gharib, Farrokh

    2011-12-01

    The solvatochromic properties of the free base and the protonated 5, 10, 15, 20-tetrakis(4-sulfonatophenyl)porphyrin (TPPS) were studied in pure water, methanol, ethanol (protic solvents), dimethylsulfoxide, DMSO, (non-protic solvent), and their corresponding aqueous-organic binary mixed solvents. The correlation of the empirical solvent polarity scale ( ET) values of TPPS with composition of the solvents was analyzed by the solvent exchange model of Bosch and Roses to clarify the preferential solvation of the probe dyes in the binary mixed solvents. The solvation shell composition and the synergistic effects in preferential solvation of the solute dyes were investigated in terms of both solvent-solvent and solute-solvent interactions and also, the local mole fraction of each solvent composition was calculated in cybotactic region of the probe. The effective mole fraction variation may provide significant physico-chemical insights in the microscopic and molecular level of interactions between TPPS species and the solvent components and therefore, can be used to interpret the solvent effect on kinetics and thermodynamics of TPPS. The obtained results from the preferential solvation and solvent-solvent interactions have been successfully applied to explain the variation of equilibrium behavior of protonation of TPPS occurring in aqueous organic mixed solvents of methanol, ethanol and DMSO.

  1. Solvation dynamics through Raman spectroscopy: hydration of Br2 and Br3(-), and solvation of Br2 in liquid bromine.

    Science.gov (United States)

    Branigan, Edward T; Halberstadt, N; Apkarian, V A

    2011-05-07

    Raman spectroscopy of bromine in the liquid phase and in water illustrates uncommon principles and yields insights regarding hydration. In liquid Br(2), resonant excitation over the B((3)Π(0u)(+)) ← X((1)Σ(g)(+)) valence transition at 532 nm produces a weak resonant Raman (RR) progression accompanied by a five-fold stronger non-resonant (NR) scattering. The latter is assigned to pre-resonance with the C-state, which in turn must be strongly mixed with inter-molecular charge transfer states. Despite the electronic resonance, RR of Br(2) in water is quenched. At 532 nm, the homogeneously broadened fundamental is observed, as in the NR case at 785 nm. The implications of the quenching of RR scattering are analyzed in a simple, semi-quantitative model, to conclude that the inertial evolution of the Raman packet in aqueous Br(2) occurs along multiple equivalent water-Br(2) coordinates. In distinct contrast with hydrophilic hydration in small clusters and hydrophobic hydration in clathrates, it is concluded that the hydration shell of bromine in water consists of dynamically equivalent fluxional water molecules. At 405 nm, the RR progression of Br(3)(-) is observed, accompanied by difference transitions between the breathing of the hydration shell and the symmetric stretch of the ion. The RR scattering process in this case can be regarded as the coherent photo-induced electron transfer to the solvent and its radiative back-transfer.

  2. Vapors produced by electronic cigarettes and e-juices with flavorings induce toxicity, oxidative stress, and inflammatory response in lung epithelial cells and in mouse lung.

    Directory of Open Access Journals (Sweden)

    Chad A Lerner

    Full Text Available Oxidative stress and inflammatory response are the key events in the pathogenesis of chronic airway diseases. The consumption of electronic cigarettes (e-cigs with a variety of e-liquids/e-juices is alarmingly increasing without the unrealized potential harmful health effects. We hypothesized that electronic nicotine delivery systems (ENDS/e-cigs pose health concerns due to oxidative toxicity and inflammatory response in lung cells exposed to their aerosols. The aerosols produced by vaporizing ENDS e-liquids exhibit oxidant reactivity suggesting oxidants or reactive oxygen species (OX/ROS may be inhaled directly into the lung during a "vaping" session. These OX/ROS are generated through activation of the heating element which is affected by heating element status (new versus used, and occurs during the process of e-liquid vaporization. Unvaporized e-liquids were oxidative in a manner dependent on flavor additives, while flavors containing sweet or fruit flavors were stronger oxidizers than tobacco flavors. In light of OX/ROS generated in ENDS e-liquids and aerosols, the effects of ENDS aerosols on tissues and cells of the lung were measured. Exposure of human airway epithelial cells (H292 in an air-liquid interface to ENDS aerosols from a popular device resulted in increased secretion of inflammatory cytokines, such as IL-6 and IL-8. Furthermore, human lung fibroblasts exhibited stress and morphological change in response to treatment with ENDS/e-liquids. These cells also secrete increased IL-8 in response to a cinnamon flavored e-liquid and are susceptible to loss of cell viability by ENDS e-liquids. Finally, exposure of wild type C57BL/6J mice to aerosols produced from a popular e-cig increase pro-inflammatory cytokines and diminished lung glutathione levels which are critical in maintaining cellular redox balance. Thus, exposure to e-cig aerosols/juices incurs measurable oxidative and inflammatory responses in lung cells and tissues that

  3. Breaking the polar-nonpolar division in solvation free energy prediction.

    Science.gov (United States)

    Wang, Bao; Wang, Chengzhang; Wu, Kedi; Wei, Guo-Wei

    2018-02-05

    Implicit solvent models divide solvation free energies into polar and nonpolar additive contributions, whereas polar and nonpolar interactions are inseparable and nonadditive. We present a feature functional theory (FFT) framework to break this ad hoc division. The essential ideas of FFT are as follows: (i) representability assumption: there exists a microscopic feature vector that can uniquely characterize and distinguish one molecule from another; (ii) feature-function relationship assumption: the macroscopic features, including solvation free energy, of a molecule is a functional of microscopic feature vectors; and (iii) similarity assumption: molecules with similar microscopic features have similar macroscopic properties, such as solvation free energies. Based on these assumptions, solvation free energy prediction is carried out in the following protocol. First, we construct a molecular microscopic feature vector that is efficient in characterizing the solvation process using quantum mechanics and Poisson-Boltzmann theory. Microscopic feature vectors are combined with macroscopic features, that is, physical observable, to form extended feature vectors. Additionally, we partition a solvation dataset into queries according to molecular compositions. Moreover, for each target molecule, we adopt a machine learning algorithm for its nearest neighbor search, based on the selected microscopic feature vectors. Finally, from the extended feature vectors of obtained nearest neighbors, we construct a functional of solvation free energy, which is employed to predict the solvation free energy of the target molecule. The proposed FFT model has been extensively validated via a large dataset of 668 molecules. The leave-one-out test gives an optimal root-mean-square error (RMSE) of 1.05 kcal/mol. FFT predictions of SAMPL0, SAMPL1, SAMPL2, SAMPL3, and SAMPL4 challenge sets deliver the RMSEs of 0.61, 1.86, 1.64, 0.86, and 1.14 kcal/mol, respectively. Using a test set of 94

  4. A simple model for solvation in mixed solvents. Applications to the stabilization and destabilization of macromolecular structures.

    Science.gov (United States)

    Schellman, J A

    1990-08-31

    The properties of a simple model for solvation in mixed solvents are explored in this paper. The model is based on the supposition that solvent replacement is a simple one-for-one substitution reaction at macromolecular sites which are independent of one another. This leads to a new form for the binding polynomial in which all terms are associated with ligand interchange rather than ligand addition. The principal solvent acts as one of the ligands. Thermodynamic analysis then shows that thermodynamic binding (i.e., selective interaction) depends on the properties of K'-1, whereas stoichiometric binding (site occupation) depends on K'. K' is a 'practical' interchange equilibrium constant given by (f3/f1)K, where K is the true equilibrium constant for the interchange of components 3 and 1 on the site and f3 and f4 denote their respective activity coefficients on the mole fraction scale. Values of K' less than unity lead to negative selective interaction. It is selective interaction and not occupation number which determines the thermodynamic effects of solvation. When K' greater than 100 on the mole fraction scale or K' greater than 2 on the molality scale (in water), the differences between stoichiometric binding and selective interaction become less than 1%. The theory of this paper is therefore necessary only for very weak binding constants. When K'-1 is small, large concentrations of the added solvent component are required to produce a thermodynamic effect. Under these circumstances the isotherms for the selective interaction and for the excess (or transfer) free energy are strongly dependent on the behavior of the activity coefficients of both solvent components. Two classes of behavior are described depending on whether the components display positive or negative deviations from Raoult's law. Examples which are discussed are aqueous solutions of urea and guanidinium chloride for positive deviations and of sucrose and glucose for negative deviations

  5. Hydrophilic Solvation Dominates the Terahertz Fingerprint of Amino Acids in Water.

    Science.gov (United States)

    Esser, Alexander; Forbert, Harald; Sebastiani, Federico; Schwaab, Gerhard; Havenith, Martina; Marx, Dominik

    2018-02-01

    Spectroscopy in the terahertz frequency regime is a sensitive tool to probe solvation-induced effects in aqueous solutions. Yet, a systematic understanding of spectral lineshapes as a result of distinct solvation contributions remains terra incognita. We demonstrate that modularization of amino acids in terms of functional groups allows us to compute their distinct contributions to the total terahertz response. Introducing the molecular cross-correlation analysis method provides unique access to these site-specific contributions. Equivalent groups in different amino acids lead to look-alike spectral contributions, whereas side chains cause characteristic but additive complexities. Specifically, hydrophilic solvation of the zwitterionic groups in valine and glycine leads to similar terahertz responses which are fully decoupled from the side chain. The terahertz response due to H-bonding within the large hydrophobic solvation shell of valine turns out to be nearly indistinguishable from that in bulk water in direct comparison to the changes imposed by the charged functional groups that form strong H-bonds with their hydration shells. Thus, the hydrophilic groups and their solvation shells dominate the terahertz absorption difference, while on the same intensity scale, the influence of hydrophobic water can be neglected.

  6. Electrostatic solvation free energies of charged hard spheres using molecular dynamics with density functional theory interactions

    Science.gov (United States)

    Duignan, Timothy T.; Baer, Marcel D.; Schenter, Gregory K.; Mundy, Chistopher J.

    2017-10-01

    Determining the solvation free energies of single ions in water is one of the most fundamental problems in physical chemistry and yet many unresolved questions remain. In particular, the ability to decompose the solvation free energy into simple and intuitive contributions will have important implications for models of electrolyte solution. Here, we provide definitions of the various types of single ion solvation free energies based on different simulation protocols. We calculate solvation free energies of charged hard spheres using density functional theory interaction potentials with molecular dynamics simulation and isolate the effects of charge and cavitation, comparing to the Born (linear response) model. We show that using uncorrected Ewald summation leads to unphysical values for the single ion solvation free energy and that charging free energies for cations are approximately linear as a function of charge but that there is a small non-linearity for small anions. The charge hydration asymmetry for hard spheres, determined with quantum mechanics, is much larger than for the analogous real ions. This suggests that real ions, particularly anions, are significantly more complex than simple charged hard spheres, a commonly employed representation.

  7. Solvation pressure as real pressure: I. Ethanol and starch under negative pressure

    CERN Document Server

    Uden, N W A V; Faux, D A; Tanczos, A C; Howlin, B; Dunstan, D J

    2003-01-01

    The reality of the solvation pressure generated by the cohesive energy density of liquids is demonstrated by three methods. Firstly, the Raman spectrum of ethanol as a function of cohesive energy density (solvation pressure) in ethanol-water and ethanol-chloroform mixtures is compared with the Raman spectrum of pure ethanol under external hydrostatic pressure and the solvation pressure and hydrostatic pressure are found to be equivalent for some transitions. Secondly, the bond lengths of ethanol are calculated by molecular dynamics modelling for liquid ethanol under pressure and for ethanol vapour. The difference in bond lengths between vapour and liquid are found to be equivalent to the solvation pressure for the C-H sub 3 , C-H sub 2 and O-H bond lengths, with discrepancies for the C-C and C-O bond lengths. Thirdly, the pressure-induced gelation of potato starch is measured in pure water and in mixtures of water and ethanol. The phase transition pressure varies in accordance with the change in solvation pre...

  8. Improving accuracy of electrochemical capacitance and solvation energetics in first-principles calculations

    Science.gov (United States)

    Sundararaman, Ravishankar; Letchworth-Weaver, Kendra; Schwarz, Kathleen A.

    2018-04-01

    Reliable first-principles calculations of electrochemical processes require accurate prediction of the interfacial capacitance, a challenge for current computationally efficient continuum solvation methodologies. We develop a model for the double layer of a metallic electrode that reproduces the features of the experimental capacitance of Ag(100) in a non-adsorbing, aqueous electrolyte, including a broad hump in the capacitance near the potential of zero charge and a dip in the capacitance under conditions of low ionic strength. Using this model, we identify the necessary characteristics of a solvation model suitable for first-principles electrochemistry of metal surfaces in non-adsorbing, aqueous electrolytes: dielectric and ionic nonlinearity, and a dielectric-only region at the interface. The dielectric nonlinearity, caused by the saturation of dipole rotational response in water, creates the capacitance hump, while ionic nonlinearity, caused by the compactness of the diffuse layer, generates the capacitance dip seen at low ionic strength. We show that none of the previously developed solvation models simultaneously meet all these criteria. We design the nonlinear electrochemical soft-sphere solvation model which both captures the capacitance features observed experimentally and serves as a general-purpose continuum solvation model.

  9. Multiconfigurational self-consistent reaction field theory for nonequilibrium solvation

    DEFF Research Database (Denmark)

    Mikkelsen, Kurt V.; Cesar, Amary; Ågren, Hans

    1995-01-01

    electronic structure whereas the inertial polarization vector is not necessarily in equilibrium with the actual electronic structure. The electronic structure of the compound is described by a correlated electronic wave function - a multiconfigurational self-consistent field (MCSCF) wave function. This wave......, open-shell, excited, and transition states. We demonstrate the theory by computing solvatochromatic shifts in optical/UV spectra of some small molecules and electron ionization and electron detachment energies of the benzene molecule. It is shown that the dependency of the solvent induced affinity...

  10. Solvation of fluoroform and fluoroform-dimethylether dimer in liquid krypton: a theoretical cryospectroscopic study.

    Science.gov (United States)

    Kohls, Emilija; Mishev, Anastas; Pejov, Ljupčo

    2013-08-07

    A hybrid, sequential statistical physics-quantum mechanical electronic-quantum mechanical nuclei approach has been applied to study the C-H stretching frequencies of bare fluoroform dissolved in liquid krypton under cryogenic conditions (at ~130 K), as well as upon blue shifting hydrogen bonding interactions with dimethylether in the same solvent. The structure of the liquid at 130 K was generated by Monte Carlo simulations of cryogenic Kr solutions containing either fluoroform or fluoroform and dimethylether molecules. Statistically uncorrelated configurations were appropriately chosen from the equilibrated MC runs and supermolecular clusters containing solute and solvent molecules (either standalone or embedded in the "bulk" part of the solvent treated as a polarizable continuum) were subjected to quantum mechanical electronic (QMel) and subsequent quantum mechanical nuclei (QMnuc) calculations. QMel calculations were implemented to generate the in-liquid 1D intramolecular C-H stretching vibrational potential of the fluoroform moiety and subsequently in the QMnuc phase the corresponding anharmonic C-H stretching frequency was computed by diagonalization techniques. Finally, the constructed vibrational density of states histograms were compared to the experimental Raman bands. The calculated anharmonic vibrational frequency shifts of the fluoroform C-H stretching mode upon interaction with dimethylether in liquid Kr are in very good agreement with the experimental data (20.3 at MP2 level vs. 16.6 cm(-1) experimentally). Most of this relatively large frequency blue shift is governed by configurations characterized by a direct C-H···O contact between monomers. The second population detected during MC simulations, characterized by reversed orientation of the monomers, has a minor contribution to the spectral appearance. The experimentally observed trend in the corresponding bandwidths is also correctly reproduced by our theoretical approach. Solvation of the

  11. Competitive solvation of (bis)(trifluoromethanesulfonyl)imide anion by acetonitrile and water

    Science.gov (United States)

    Chaban, Vitaly

    2014-10-01

    Competitive solvation of an ion by two or more solvents is one of the key phenomena determining the identity of our world. Solvation in polar solvents frequently originates from non-additive non-covalent interactions. Pre-parametrized potentials poorly capture these interactions, unless the force field derivation is repeated for every new system. Development cost increases drastically as new chemical species are supplied. This work represents an alternative simulation approach, PM7-MD, by coupling the latest semiempirical parametrization, PM7, with equation-of-motion propagation scheme and temperature coupling. Using a competitive solvation of (bis)(trifluoromethanesulfonyl)imide anion in acetonitrile and water, the work demonstrates efficiency and robustness of PM7-MD.

  12. Solvation of decane and benzene in mixtures of 1-octanol and N, N-dimethylformamide

    Science.gov (United States)

    Kustov, A. V.; Smirnova, N. L.

    2016-09-01

    The heats of dissolution of decane and benzene in a model system of octanol-1 (OctOH) and N, N-dimethylformamide (DMF) at 308 K are measured using a variable temperature calorimeter equipped with an isothermal shell. Standard enthalpies are determined and standard heat capacities of dissolution in the temperature range of 298-318 K are calculated using data obtained in [1, 2]. The state of hydrocarbon molecules in a binary mixture is studied in terms of the enhanced coordination model (ECM). Benzene is shown to be preferentially solvated by DMF over the range of physiological temperatures. The solvation shell of decane is found to be strongly enriched with 1-octanol. It is obvious that although both hydrocarbons are nonpolar, the presence of the aromatic π-system in benzene leads to drastic differences in their solvation in a lipid-protein medium.

  13. Analysis of biomolecular solvation sites by 3D-RISM theory.

    Science.gov (United States)

    Sindhikara, Daniel J; Hirata, Fumio

    2013-06-06

    We derive, implement, and apply equilibrium solvation site analysis for biomolecules. Our method utilizes 3D-RISM calculations to quickly obtain equilibrium solvent distributions without either necessity of simulation or limits of solvent sampling. Our analysis of these distributions extracts highest likelihood poses of solvent as well as localized entropies, enthalpies, and solvation free energies. We demonstrate our method on a structure of HIV-1 protease where excellent structural and thermodynamic data are available for comparison. Our results, obtained within minutes, show systematic agreement with available experimental data. Further, our results are in good agreement with established simulation-based solvent analysis methods. This method can be used not only for visual analysis of active site solvation but also for virtual screening methods and experimental refinement.

  14. Solvation of monovalent anions in formamide and methanol: Parameterization of the IEF-PCM model

    International Nuclear Information System (INIS)

    Boees, Elvis S.; Bernardi, Edson; Stassen, Hubert; Goncalves, Paulo F.B.

    2008-01-01

    The thermodynamics of solvation for a series of monovalent anions in formamide and methanol has been studied using the polarizable continuum model (PCM). The parameterization of this continuum model was guided by molecular dynamics simulations. The parameterized PCM model predicts the Gibbs free energies of solvation for 13 anions in formamide and 16 anions in methanol in very good agreement with experimental data. Two sets of atomic radii were tested in the definition of the solute cavities in the PCM and their performances are evaluated and discussed. Mean absolute deviations of the calculated free energies of solvation from the experimental values are in the range of 1.3-2.1 kcal/mol

  15. Quantitative measurement of solvation shells using frequency modulated atomic force microscopy

    Science.gov (United States)

    Uchihashi, T.; Higgins, M.; Nakayama, Y.; Sader, J. E.; Jarvis, S. P.

    2005-03-01

    The nanoscale specificity of interaction measurements and additional imaging capability of the atomic force microscope make it an ideal technique for measuring solvation shells in a variety of liquids next to a range of materials. Unfortunately, the widespread use of atomic force microscopy for the measurement of solvation shells has been limited by uncertainties over the dimensions, composition and durability of the tip during the measurements, and problems associated with quantitative force calibration of the most sensitive dynamic measurement techniques. We address both these issues by the combined use of carbon nanotube high aspect ratio probes and quantifying the highly sensitive frequency modulation (FM) detection technique using a recently developed analytical method. Due to the excellent reproducibility of the measurement technique, additional information regarding solvation shell size as a function of proximity to the surface has been obtained for two very different liquids. Further, it has been possible to identify differences between chemical and geometrical effects in the chosen systems.

  16. Solvation phenomena in association theories with applications to oil & gas and chemical industries

    DEFF Research Database (Denmark)

    Kontogeorgis, Georgios; Folas, Georgios; Muro Sunè, Nuria

    2008-01-01

    Association theories e.g. those belonging to the SAFT family account explicitly for self- and cross-association (solvation) phenomena. Such phenomena are of great practical importance as they affect, often dramatically, the phase behaviour of many mixtures of industrial relevance. From the scient......Association theories e.g. those belonging to the SAFT family account explicitly for self- and cross-association (solvation) phenomena. Such phenomena are of great practical importance as they affect, often dramatically, the phase behaviour of many mixtures of industrial relevance. From...

  17. Phase Equilibria and Ionic Solvation in the Lithium Tetrafluoroborate-Dimethylsulfoxide System

    Science.gov (United States)

    Gafurov, M. M.; Kirillov, S. A.; Gorobets, M. I.; Rabadanov, K. Sh.; Ataev, M. B.; Tretyakov, D. O.; Aydemirov, K. M.

    2015-01-01

    The phase diagram and electrical conductivity isotherms for the lithium tetrafluoroborate (LiBF4)-dimethylsulfoxide (DMSO) system and Raman spectra of DMSO and the LiBF4-DMSO solution were studied. Spectroscopic signatures of a H-bond between DMSO and BF4 - ions were found. The bonds of Li+ ions to the solvent were stronger than the bonds in DMSO dimers because formation of the solvate destroyed dimeric DMSO molecules. The τω values for DMSO molecules in the Li+-ion solvate shell of the LiBF4-DMSO system were similar to those for associated solvent molecules.

  18. Modelos contínuos do solvente: fundamentos Continuum solvation models: fundamentals

    Directory of Open Access Journals (Sweden)

    Josefredo R. Pliego Jr

    2006-06-01

    Full Text Available Continuum solvation models are nowadays widely used in the modeling of solvent effects and the range of applications goes from the calculation of partition coefficients to chemical reactions in solution. The present work presents a detailed explanation of the physical foundations of continuum models. We discuss the polarization of a dielectric and its representation through the volume and surface polarization charges. The Poisson equation for a dielectric was obtained and we have also derived and discuss the apparent surface charge method and its application for free energy of solvation calculations.

  19. Spectral luminescence studies of eosin solvation in water-alcohol mixtures

    Energy Technology Data Exchange (ETDEWEB)

    Ketsle, G.A.; Levshin, L.V.; Mel' nikov, G.V.; Saletskii, A.M.

    1987-11-01

    The authors investigate the effects of solvation of eosin molecules in binary water-propanol mixtures with the goal of assessing eosin as a candidate dye laser material. The fluorescence was measured with a Hitachi spectrofluorimeter and the absorption spectra were taken on a Specord spectrophotometer. Absorption and fluorescence were measured for different amounts of propanol in the solvent. Data are also given on excitation and de-excitation kinetics between ground and excited states. Values for quantum yields of fluorescence and phosphorescence, average excited state lifetime, and molecular volume of the dye with the solvated shell are tabulated.

  20. Preferential Solvation of Silver (I) Bromate in Methanol-Dimethylsulfoxide Mixtures

    Science.gov (United States)

    Janardhanan, S.; Kalidas, C.

    1984-06-01

    The solubiltiy of silver bromate, the Gibbs transfer energy of Ag+ and BrO3- and the solvent transport number in methanol-dimethyl sulfoxide mixtures are reported. The solubility of silver bromate increases with addition of DMSO. The Gibbs energy of transfer of the silver ion (based on the ferrocene reference method) decreases, while that of the bromate ion becomes slightly negative with the addition of DMSO. The solvent transport number A passes through a maximum (⊿ = 1.0 at XDMSO = 0.65. From these results, it is concluded that the silver ion is preferentially solvated by DMSO whereas the bromate ion shows no preferential solvation.

  1. Are mixed explicit/implicit solvation models reliable for studying phosphate hydrolysis? A comparative study of continuum, explicit and mixed solvation models.

    Energy Technology Data Exchange (ETDEWEB)

    Kamerlin, Shina C. L.; Haranczyk, Maciej; Warshel, Arieh

    2009-05-01

    Phosphate hydrolysis is ubiquitous in biology. However, despite intensive research on this class of reactions, the precise nature of the reaction mechanism remains controversial. In this work, we have examined the hydrolysis of three homologous phosphate diesters. The solvation free energy was simulated by means of either an implicit solvation model (COSMO), hybrid quantum mechanical / molecular mechanical free energy perturbation (QM/MM-FEP) or a mixed solvation model in which N water molecules were explicitly included in the ab initio description of the reacting system (where N=1-3), with the remainder of the solvent being implicitly modelled as a continuum. Here, both COSMO and QM/MM-FEP reproduce Delta Gobs within an error of about 2kcal/mol. However, we demonstrate that in order to obtain any form of reliable results from a mixed model, it is essential to carefully select the explicit water molecules from short QM/MM runs that act as a model for the true infinite system. Additionally, the mixed models tend to be increasingly inaccurate the more explicit water molecules are placed into the system. Thus, our analysis indicates that this approach provides an unreliable way for modelling phosphate hydrolysis in solution.

  2. Electron detector

    International Nuclear Information System (INIS)

    Hashimoto, H.; Mogami, A.

    1975-01-01

    A device for measuring electron densities at a given energy level in an electron beam or the like having strong background noise, for example, in the detection of Auger electric energy spectrums is described. An electron analyzer passes electrons at the given energy level and at the same time electrons of at least one adjacent energy level. Detecting means associated therewith produce signals indicative of the densities of the electrons at each energy level and combine these signals to produce a signal indicative of the density of the electrons of the given energy level absent background noise

  3. Preferential solvation, ion pairing, and dynamics of concentrated aqueous solutions of divalent metal nitrate salts

    Science.gov (United States)

    Yadav, Sushma; Chandra, Amalendu

    2017-12-01

    We have investigated the characteristics of preferential solvation of ions, structure of solvation shells, ion pairing, and dynamics of aqueous solutions of divalent alkaline-earth metal nitrate salts at varying concentration by means of molecular dynamics simulations. Hydration shell structures and the extent of preferential solvation of the metal and nitrate ions in the solutions are investigated through calculations of radial distribution functions, tetrahedral ordering, and also spatial distribution functions. The Mg2+ ions are found to form solvent separated ion-pairs while the Ca2+ and Sr2+ ions form contact ion pairs with the nitrate ions. These findings are further corroborated by excess coordination numbers calculated through Kirkwood-Buff G factors for different ion-ion and ion-water pairs. The ion-pairing propensity is found to be in the order of Mg(NO3) 2 lead to the presence of substantial dynamical heterogeneity in these solutions of strongly interacting ions. The current study helps us to understand the molecular details of hydration structure, ion pairing, and dynamics of water in the solvation shells and also of ion diffusion in aqueous solutions of divalent metal nitrate salts.

  4. Affine-response model of molecular solvation of ions: Accurate predictions of asymmetric charging free energies

    Czech Academy of Sciences Publication Activity Database

    Bardhan, J. P.; Jungwirth, Pavel; Makowski, L.

    Roč. 137, č. 12 ( 2012 ), 124101/1-124101/6 ISSN 0021-9606 R&D Projects: GA MŠk LH12001 Institutional research plan: CEZ:AV0Z40550506 Keywords : ion solvation * continuum models * linear response Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.164, year: 2012

  5. Mutagenicity of Tween 80-solvated mild gasification products in the Ames salmonella microsomal assay system

    Energy Technology Data Exchange (ETDEWEB)

    1992-01-13

    The results of the Tween 80-solvated Ames testing of six mild gasification samples indicate significant mutagenic activity only in the composite materials (MG-119 and MG-120), previously suspected from the DMSO-solvated assays, which had shown some variable but ultimately insignificant mutagenic responses. The activity of these samples from the Tween 80-solvated assays was quite low when compared to either the positive controls or the SRC-II HD coal-liquefaction reference material. The class of mutagenic activity expressed by these samples solvated in Tween 80 was that of an indirect-acting, frameshift mutagen(s) since significant activity was found only on tester strain TA98 in the presence of the metabolic activation fraction (S9). Because DMSO and other solvents have been shown to affect the mutagenic activity of certain pure chemicals, the possibility of solvent/mutagen interactions in complex mixtures such as coal-derived liquids exists. Thus, the testing of the genotoxic activity of undefined, chemically complex compounds may require the use of at least two solvent systems to reduce the possibility of artifactual findings. 10 refs., 4 tabs.

  6. Ni(salen): a system that forms many solvates with interacting Ni atoms

    NARCIS (Netherlands)

    Siegler, M.A.M.; Lutz, M.

    2009-01-01

    Recrystallization of [N,N’-Ethylene-bis(salicylideneiminato)]-nickel(II) [Ni(salen)] has been carried out from a large selection of solvents. Crystals can be either solvent free or solvates. This study is based on X-ray crystal structure determinations, which include the redetermination of Ni(salen)

  7. Conformational Behavior of Polymer Chains of Different Architectures in Strongly Endothermic Solvent Mixtures: Specific Solvation Effects.

    Czech Academy of Sciences Publication Activity Database

    Suchá, L.; Limpouchová, Z.; Procházka, Karel

    2017-01-01

    Roč. 295, č. 8 (2017), s. 1391-1403 ISSN 0303-402X R&D Projects: GA ČR GA15-19542S Institutional support: RVO:67985858 Keywords : cononsolvency * preferential solvation * star polymer Subject RIV: CF - Physical ; Theoretical Chemistry OBOR OECD: Physical chemistry Impact factor: 1.723, year: 2016

  8. Influence of temperature and molecular structure on ionic liquid solvation layers.

    Science.gov (United States)

    Wakeham, Deborah; Hayes, Robert; Warr, Gregory G; Atkin, Rob

    2009-04-30

    Atomic force microscopy (AFM) force profiling is used to investigate the structure of adsorbed and solvation layers formed on a mica surface by various room temperature ionic liquids (ILs) ethylammonium nitrate (EAN), ethanolammonium nitrate (EtAN), ethylammonium formate (EAF), propylammonium formate (PAF), ethylmethylammonium formate (EMAF), and dimethylethylammonium formate (DMEAF). At least seven layers are observed for EAN at 14 degrees C (melting point 13 degrees C), decreasing as the temperature is increased to 30 degrees C due to thermal energy disrupting solvophobic forces that lead to segregation of cation alkyl tails from the charged ammonium and nitrate moieties. The number and properties of the solvation layers can also be controlled by introducing an alcohol moiety to the cation's alkyl tail (EtAN), or by replacing the nitrate anion with formate (EAF and PAF), even leading to the detection of distinct cation and anion sublayers. Substitution of primary by secondary or tertiary ammonium cations reduces the number of solvation layers formed, and also weakens the cation layer adsorbed onto mica. The observed solvation and adsorbed layer structures are discussed in terms of the intermolecular cohesive forces within the ILs.

  9. Strong Stretching of Poly(ethylene glycol) Brushes Mediated by Ionic Liquid Solvation.

    Science.gov (United States)

    Han, Mengwei; Espinosa-Marzal, Rosa M

    2017-09-07

    We have measured forces between mica surfaces coated with a poly(ethylene glycol) (PEG) brush solvated by a vacuum-dry ionic liquid, 1-ethyl-3-methyl imidazolium bis(trifluoromethylsulfonyl)imide, with a surface forces apparatus. At high grafting density, the solvation mediated by the ionic liquid causes the brush to stretch twice as much as in water. Modeling of the steric repulsion indicates that PEG behaves as a polyelectrolyte; the hydrogen bonding between ethylene glycol and the imidazolium cation seems to effectively charge the polymer brush, which justifies the strong stretching. Importantly, under strong polymer compression, solvation layers are squeezed out at a higher rate than for the neat ionic liquid. We propose that the thermal fluctuations of the PEG chains, larger in the brush than in the mushroom configuration, maintain the fluidity of the ionic liquid under strong compression, in contrast to the solid-like squeezing-out behavior of the neat ionic liquid. This is the first experimental study of the behavior of a polymer brush solvated by an ionic liquid under nanoconfinement.

  10. Fluorescent probe studies of polarity and solvation within room temperature ionic liquids: a review.

    Science.gov (United States)

    Pandey, Shubha; Baker, Sheila N; Pandey, Siddharth; Baker, Gary A

    2012-09-01

    Ionic liquids display an array of useful and sometimes unconventional, solvent features and have attracted considerable interest in the field of green chemistry for the potential they hold to significantly reduce environmental emissions. Some of these points have a bearing on the chemical reactivity of these systems and have also generated interest in the physical and theoretical aspects of solvation in ionic liquids. This review presents an introduction to the field of ionic liquids, followed by discussion of investigations into the solvation properties of neat ionic liquids or mixed systems including ionic liquids as a major or minor component. The ionic liquid based multicomponent systems discussed are composed of other solvents, other ionic liquids, carbon dioxide, surfactants or surfactant solutions. Although we clearly focus on fluorescence spectroscopy as a tool to illuminate ionic liquid systems, the issues discussed herein are of general relevance to discussions of polarity and solvent effects in ionic liquids. Transient solvation measurements carried out by means of time-resolved fluorescence measurements are particularly powerful for their ability to parameterize the kinetics of the solvation process in ionic liquids and are discussed as well.

  11. Highly Stable Lithium Metal Batteries Enabled by Regulating the Solvation of Lithium Ions in Nonaqueous Electrolytes.

    Science.gov (United States)

    Zhang, Xue-Qiang; Chen, Xiang; Cheng, Xin-Bing; Li, Bo-Quan; Shen, Xin; Yan, Chong; Huang, Jia-Qi; Zhang, Qiang

    2018-05-04

    Safe and rechargeable lithium metal batteries have been difficult to achieve because of the formation of lithium dendrites. Herein an emerging electrolyte based on a simple solvation strategy is proposed for highly stable lithium metal anodes in both coin and pouch cells. Fluoroethylene carbonate (FEC) and lithium nitrate (LiNO 3 ) were concurrently introduced into an electrolyte, thus altering the solvation sheath of lithium ions, and forming a uniform solid electrolyte interphase (SEI), with an abundance of LiF and LiN x O y on a working lithium metal anode with dendrite-free lithium deposition. Ultrahigh Coulombic efficiency (99.96 %) and long lifespans (1000 cycles) were achieved when the FEC/LiNO 3 electrolyte was applied in working batteries. The solvation chemistry of electrolyte was further explored by molecular dynamics simulations and first-principles calculations. This work provides insight into understanding the critical role of the solvation of lithium ions in forming the SEI and delivering an effective route to optimize electrolytes for safe lithium metal batteries. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Applications of the solvation parameter model in reversed-phase liquid chromatography.

    Science.gov (United States)

    Poole, Colin F; Lenca, Nicole

    2017-02-24

    The solvation parameter model is widely used to provide insight into the retention mechanism in reversed-phase liquid chromatography, for column characterization, and in the development of surrogate chromatographic models for biopartitioning processes. The properties of the separation system are described by five system constants representing all possible intermolecular interactions for neutral molecules. The general model can be extended to include ions and enantiomers by adding new descriptors to encode the specific properties of these compounds. System maps provide a comprehensive overview of the separation system as a function of mobile phase composition and/or temperature for method development. The solvation parameter model has been applied to gradient elution separations but here theory and practice suggest a cautious approach since the interpretation of system and compound properties derived from its use are approximate. A growing application of the solvation parameter model in reversed-phase liquid chromatography is the screening of surrogate chromatographic systems for estimating biopartitioning properties. Throughout the discussion of the above topics success as well as known and likely deficiencies of the solvation parameter model are described with an emphasis on the role of the heterogeneous properties of the interphase region on the interpretation and understanding of the general retention mechanism in reversed-phase liquid chromatography for porous chemically bonded sorbents. Copyright © 2016 Elsevier B.V. All rights reserved.

  13. Solvated protein-protein docking using Kyte-Doolittle-based water preferences

    NARCIS (Netherlands)

    Kastritis, P.; Visscher, K.M.; van Dijk, A.D.J.; Bonvin, A.M.J.J.

    2013-01-01

    HADDOCK is one of the few docking programs that can explicitly account for water molecules in the docking process. Its solvated docking protocol starts from hydrated molecules and a fraction of the resulting interfacial waters is subsequently removed in a biased Monte Carlo procedure based on

  14. Solvated protein-protein docking using Kyte-Doolittle-based water preferences

    NARCIS (Netherlands)

    Kastritis, Panagiotis L.; Visscher, Koen M.; van Dijk, Aalt D.J.; Bonvin, Alexandre M.J.J.

    HADDOCK is one of the few docking programs that can explicitly account for water molecules in the docking process. Its solvated docking protocol starts from hydrated molecules and a fraction of the resulting interfacial waters is subsequently removed in a biased Monte Carlo procedure based on

  15. Systematic solvate screening of trospium chloride: discovering hydrates of a long-established pharmaceutical

    Czech Academy of Sciences Publication Activity Database

    Sládková, V.; Skalická, T.; Skořepová, E.; Čejka, J.; Eigner, Václav; Kratochvíl, B.

    2015-01-01

    Roč. 17, č. 25 (2015), s. 4712-4721 ISSN 1466-8033 R&D Projects: GA ČR(CZ) GA14-03276S Institutional support: RVO:68378271 Keywords : trospium chloride * solvate screening * x-ray crystallography * Jana2006 Subject RIV: FR - Pharmacology ; Medidal Chemistry Impact factor: 3.849, year: 2015

  16. Solvation in atomic liquids: connection between Gaussian field theory and density functional theory

    Directory of Open Access Journals (Sweden)

    V. Sergiievskyi

    2017-12-01

    Full Text Available For the problem of molecular solvation, formulated as a liquid submitted to the external potential field created by a molecular solute of arbitrary shape dissolved in that solvent, we draw a connection between the Gaussian field theory derived by David Chandler [Phys. Rev. E, 1993, 48, 2898] and classical density functional theory. We show that Chandler's results concerning the solvation of a hard core of arbitrary shape can be recovered by either minimising a linearised HNC functional using an auxiliary Lagrange multiplier field to impose a vanishing density inside the core, or by minimising this functional directly outside the core — indeed a simpler procedure. Those equivalent approaches are compared to two other variants of DFT, either in the HNC, or partially linearised HNC approximation, for the solvation of a Lennard-Jones solute of increasing size in a Lennard-Jones solvent. Compared to Monte-Carlo simulations, all those theories give acceptable results for the inhomogeneous solvent structure, but are completely out-of-range for the solvation free-energies. This can be fixed in DFT by adding a hard-sphere bridge correction to the HNC functional.

  17. Solvated Positron Chemistry. Competitive Positron Reactions with Halide Ions in Water

    DEFF Research Database (Denmark)

    Christensen, Palle; Pedersen, Niels Jørgen; Andersen, J. R.

    1979-01-01

    It is shown by means of the angular correlation technique that the binding of positrons to halides is strongly influenced by solvation effects. For aqueous solutions we find increasing values for the binding energies between the halide and the positron with increasing mass of the halide...

  18. Febuxostat-Minoxidil Salt Solvates: Crystal Structures, Characterization, Interconversion and Solubility Performance

    Directory of Open Access Journals (Sweden)

    Li-Yang Li

    2018-02-01

    Full Text Available Three febuxostat-minoxidil salt solvates with acetone (ACE, tetrahydrofuran (THF and isopropanol (IPA are synthesized by solvent-assisted grinding and characterized by infrared (IR, nuclear magnetic resonance (1H-NMR, single crystal and powder X-ray diffraction (PXRD, thermogravimetry (TG and differential scanning calorimetry (DSC. These febuxostat-minoxidil salt solvates feature isostructural with the same stoichiometries (1:1:1 molecule ratio. The proton transfers from the carboxylic group of febuxostat (FEB to imino N atom of minoxidil (MIN, which forms the motif with combined R 2 2 (9 R 4 2 (8 R 2 2 (9 graph set in the three solvates. The solvents occupy the different positions related to the motif, which results in the apparent differences in PXRD patterns before/after desolvation although they are isostructures. The FEB-MIN·THF was more thermostable than FEB-MIN·ACE and FEB-MIN·IPA relative to solvent removal from DSC patterns, which is different from the results from the solvent-exchange experiments in chemical kinetics. All three salt solvates exhibit increased equilibrium solubility compared to FEB in aqueous medium.

  19. Solvation analysis of some Solvatochromic probes in binary mixtures of reline, ethaline, and glyceline with DMSO

    Czech Academy of Sciences Publication Activity Database

    Harifi-Mood, A.R.; Ghobadi, R.; Matić, S.; Minofar, Babak; Řeha, David

    2016-01-01

    Roč. 22, OCT 2016 (2016), s. 845-853 ISSN 0167-7322 R&D Projects: GA ČR GA13-21053S; GA MŠk(CZ) LM2015055 Institutional support: RVO:61388971 Keywords : Deep eutectic solvents * Solvatochromic parameters * Preferential solvation Subject RIV: EE - Microbiology, Virology Impact factor: 3.648, year: 2016

  20. Solvent density inhomogeneities and solvation free energies in supercritical diatomic fluids: a density functional approach.

    Science.gov (United States)

    Husowitz, B; Talanquer, V

    2007-02-07

    Density functional theory is used to explore the solvation properties of a spherical solute immersed in a supercritical diatomic fluid. The solute is modeled as a hard core Yukawa particle surrounded by a diatomic Lennard-Jones fluid represented by two fused tangent spheres using an interaction site approximation. The authors' approach is particularly suitable for thoroughly exploring the effect of different interaction parameters, such as solute-solvent interaction strength and range, solvent-solvent long-range interactions, and particle size, on the local solvent structure and the solvation free energy under supercritical conditions. Their results indicate that the behavior of the local coordination number in homonuclear diatomic fluids follows trends similar to those reported in previous studies for monatomic fluids. The local density augmentation is particularly sensitive to changes in solute size and is affected to a lesser degree by variations in the solute-solvent interaction strength and range. The associated solvation free energies exhibit a nonmonotonous behavior as a function of density for systems with weak solute-solvent interactions. The authors' results suggest that solute-solvent interaction anisotropies have a major influence on the nature and extent of local solvent density inhomogeneities and on the value of the solvation free energies in supercritical solutions of heteronuclear molecules.

  1. Effect of Preferential Solvation of Polymer Chains on Vapor-Pressure Osmometry Results. Computer Simulation Study.

    Czech Academy of Sciences Publication Activity Database

    Svoboda, Martin; Lísal, Martin; Limpouchová, Z.; Procházka, Karel

    2018-01-01

    Roč. 23, č. 3 (2018), s. 244-251 ISSN 1023-666X R&D Projects: GA ČR GA15-19542S Institutional support: RVO:67985858 Keywords : vapor-pressure osmometry * simulation * solvatation Subject RIV: CF - Physical ; Theoretical Chemistry OBOR OECD: Physical chemistry

  2. Comparative assessment of computational methods for the determination of solvation free energies in alcohol-based molecules.

    Science.gov (United States)

    Martins, Silvia A; Sousa, Sergio F

    2013-06-05

    The determination of differences in solvation free energies between related drug molecules remains an important challenge in computational drug optimization, when fast and accurate calculation of differences in binding free energy are required. In this study, we have evaluated the performance of five commonly used polarized continuum model (PCM) methodologies in the determination of solvation free energies for 53 typical alcohol and alkane small molecules. In addition, the performance of these PCM methods, of a thermodynamic integration (TI) protocol and of the Poisson-Boltzmann (PB) and generalized Born (GB) methods, were tested in the determination of solvation free energies changes for 28 common alkane-alcohol transformations, by the substitution of an hydrogen atom for a hydroxyl substituent. The results show that the solvation model D (SMD) performs better among the PCM-based approaches in estimating solvation free energies for alcohol molecules, and solvation free energy changes for alkane-alcohol transformations, with an average error below 1 kcal/mol for both quantities. However, for the determination of solvation free energy changes on alkane-alcohol transformation, PB and TI yielded better results. TI was particularly accurate in the treatment of hydroxyl groups additions to aromatic rings (0.53 kcal/mol), a common transformation when optimizing drug-binding in computer-aided drug design. Copyright © 2013 Wiley Periodicals, Inc.

  3. Absolute single-ion solvation free energy scale in methanol determined by the lithium cluster-continuum approach.

    Science.gov (United States)

    Pliego, Josefredo R; Miguel, Elizabeth L M

    2013-05-02

    Absolute solvation free energy of the lithium cation in methanol was calculated by the cluster-continuum quasichemical theory of solvation. Clusters with up to five methanol molecules were investigated using X3LYP, MP2, and MP4 methods with DZVP, 6-311+G(2df,2p), TZVPP+diff, and QZVPP+diff basis sets and including the cluster solvation through the PCM and SMD continuum models. Our calculations have determined a value of -118.1 kcal mol(-1) for the solvation free energy of the lithium, in close agreement with a value of -116.6 kcal mol(-1) consistent with the TATB assumption. Using data of solvation and transfer free energy of a pair of ions, electrode potentials and pKa, we have obtained the solvation free energy of 25 ions in methanol. Our analysis leads to a value of -253.6 kcal mol(-1) for the solvation free energy of the proton, which can be compared with the value of -263.5 kcal mol(-1) obtained by Kelly et al. using the cluster pair approximation. Considering that this difference is due to the methanol surface potential, we have estimated that it corresponds to -0.429 V.

  4. A sensitive fluorescent probe for the polar solvation dynamics at protein-surfactant interfaces.

    Science.gov (United States)

    Singh, Priya; Choudhury, Susobhan; Singha, Subhankar; Jun, Yongwoong; Chakraborty, Sandipan; Sengupta, Jhimli; Das, Ranjan; Ahn, Kyo-Han; Pal, Samir Kumar

    2017-05-17

    Relaxation dynamics at the surface of biologically important macromolecules is important taking into account their functionality in molecular recognition. Over the years it has been shown that the solvation dynamics of a fluorescent probe at biomolecular surfaces and interfaces account for the relaxation dynamics of polar residues and associated water molecules. However, the sensitivity of the dynamics depends largely on the localization and exposure of the probe. For noncovalent fluorescent probes, localization at the region of interest in addition to surface exposure is an added challenge compared to the covalently attached probes at the biological interfaces. Here we have used a synthesized donor-acceptor type dipolar fluorophore, 6-acetyl-(2-((4-hydroxycyclohexyl)(methyl)amino)naphthalene) (ACYMAN), for the investigation of the solvation dynamics of a model protein-surfactant interface. A significant structural rearrangement of a model histone protein (H1) upon interaction with anionic surfactant sodium dodecyl sulphate (SDS) as revealed from the circular dichroism (CD) studies is nicely corroborated in the solvation dynamics of the probe at the interface. The polarization gated fluorescence anisotropy of the probe compared to that at the SDS micellar surface clearly reveals the localization of the probe at the protein-surfactant interface. We have also compared the sensitivity of ACYMAN with other solvation probes including coumarin 500 (C500) and 4-(dicyanomethylene)-2-methyl-6-(p-dimethylamino-styryl)-4H-pyran (DCM). In comparison to ACYMAN, both C500 and DCM fail to probe the interfacial solvation dynamics of a model protein-surfactant interface. While C500 is found to be delocalized from the protein-surfactant interface, DCM becomes destabilized upon the formation of the interface (protein-surfactant complex). The timescales obtained from this novel probe have also been compared with other femtosecond resolved studies and molecular dynamics simulations.

  5. Time Resolved Broadband Terahertz Relaxation Dynamics of Electron in Water

    DEFF Research Database (Denmark)

    Wang, Tianwu; Iwaszczuk, Krzysztof; Cooke, David G.

    We investigated the transient response of the solvated electron in water ejected by photodetachment from potassium ferrocyanide using time resolved terahertz spectroscopy (TSTS). Ultrabroadband THz transients are generated and detected by a two-color femtosecond-induced air plasma and air biased...

  6. Electronics Industry

    National Research Council Canada - National Science Library

    Bell, Robert; Carroll-Garrison, Martina; Donovan, Daniel; Fisher, John; Guemmer, Paul; Harms, Robert; Kelly, Timothy; Love, Mattie; McReynolds, James; Ward, Ralph

    2006-01-01

    .... Government action to preserve strategic access to semiconductor producers is clearly needed to ensure DoD electronic systems can be built without compromising sensitive technology, though every...

  7. Electron Scattering by biomass molecular fragments

    Science.gov (United States)

    Lima, Marco

    2015-09-01

    The replacement of fossil fuels by biofuels from renewable sources may not be a definite answer for greenhouse gas emissions problems, but it is a good step towards a sustainable energy strategy. Few per cent of ethanol is being mixed to gasoline in many countries and in some of them, like Brazil, a very aggressive program has been developed, using, in large scale, flex fuel engines that can run with any mixture of gasoline and ethanol, including 100% ethanol. Important points are how to produce ethanol in a sustainable way and with which technology? Biomass is a good candidate to enhance the first generation (produced from Corn in USA and from sugarcane in Brazil) production towards the so-called second-generation ethanol, since it has cellulose and hemicellulose as source of sugars. In order to liberate these sugars for fermentation, it is important to learn how to separate the main components. Chemical routes (acid treatment) and biological routes (enzymatic hydrolysis) are combined and used for these purposes. Atmospheric plasmas can be useful for attacking the biomass in a controlled manner and low energy electrons may have an important role in the process. Recently, we have been studying the interaction of electrons with lignin subunits (phenol, guaiacol, p-coumaryl alcohol), cellulose components, β-D-glucose and cellobiose (β(1-4) linked glucose dimer) and hemicellulose components [2] (β-D-xylose). We also obtained results for the amylose subunits α-D-glucose and maltose (α(1-4) linked glucose dimer). Altogether, the resonance spectra of lignin, cellulose and hemicellulose components establish a physical-chemical basis for electron-induced biomass pretreatment that could be applied to biofuel production. In order to describe a more realistic system (where molecules are ``wet''), we have obtained the shape resonance spectra of phenol-water clusters, as obtained previously from elastic electron scattering calculations. Our results, obtained in a simple

  8. Coulomb focusing and path'' interference of autoionizing electrons produced in 10 keV He sup + + He collisions

    Energy Technology Data Exchange (ETDEWEB)

    Swenson, J.K. (Lawrence Livermore National Lab., CA (USA)); Burgdoerfer, J. (Tennessee Univ., Knoxville, TN (USA)); Meyer, F.W.; Havener, C.C.; Gregory, D.C.; Stolterfoht, N. (Oak Ridge National Lab., TN (USA))

    1991-03-13

    Autoionizing electrons emitted following low energy ion-atom collisions may scatter significantly from the receding spectator ion's attractive Coulomb field. In such cases the observed electron intensity is focused'' in the direction of the scattering ion as a result of the effective compression of the emission solid angle. In addition, interference may occur between trajectories, corresponding to electrons scattering around opposite sides of the ion, which lead to the same final laboratory electron energy and emission angle. This Coulomb path'' interference mechanism manifests itself in the uncharacteristically rapid angular dependence of the He target 2s{sup 2} {sup 1}S autoionizing state measured near 0{degree} following low energy He{sup +} + He collisions. A classical trajectory model for Coulomb focusing is presented and a semi-classical approximation is used to model the Coulomb path'' interference mechanism. In this description we account for the evolution of the phase of the autoionizing state until its decay and the path dependence of the amplitude of the emitted electron following decay of the autoionizing state. Calculated model lineshapes, which include contributions from adjacent overlapping resonances, reproduce quite well the angular dependence observed in the data near 0{degree}. 14 refs., 7 figs.

  9. Effect of Cl substituent in the aromatic tetracycline ring on its reactivity with solvated electrons

    Energy Technology Data Exchange (ETDEWEB)

    Dziegielewski, J O; Glowacki, P [Universytet Slaski, Katowice (Poland). Inst. Chemii; Goracy, J; Orlowska-Dudek, D; Sloma, E [Wroclaw Univ. (Poland) Inst. Chemii

    1984-09-18

    Decomposition yields of tetracycline hydrochloride (TC.HCl) and chlorotetracycline hydrochloride (ClTC.HCl) in methanol solution saturated with Ar or N/sub 2/O were determined. Rate constants of the reaction esub(s)/sup -/ with some antibiotics were obtained. It was demonstrated by /sup 1/H NMR that the radical formed by degradation of 7-C-Cl group is recombined with the H atoms leading to ClTC.HCl being converted into tetracycline hydrochloride (TC.HCl).

  10. Solvation Effects on Electronic Transitions: Exploring the Performance of Advanced Solvent Potentials in Polarizable Embedding Calculations

    DEFF Research Database (Denmark)

    Schwabe, Tobias; Olsen, Magnus; Sneskov, Kristian

    2011-01-01

    The polarizable embedding (PE) approach, which combines quantum mechanics (QM) and molecular mechanics (MM), is applied to predict solvatochromic effects on excitation energies of several representative molecules in aqueous, methanol, acetonitrile, and carbon tetrachloride solutions. Good agreement...

  11. Bis(1,3-dimethyl-1H-imidazolium hexafluorosilicate methanol 0.33-solvate

    Directory of Open Access Journals (Sweden)

    Maxim V. Borzov

    2013-08-01

    Full Text Available The title compound, 6C5H9N2+·3SiF62−·CH3OH, (I, was prepared by recrystallization of the crude salt from methanol along with solvent-free 2C5H9N2+·SiF62− (II. Crystals of these solvatomorphs can be separated manually. The solvate (I crystallizes in a rare hexagonal space group P6/mcc. Its asymmetric unit comprises one half of an imidazolium cation bisected by the crystallographic m-plane, one-sixth and one-twelfth of two crystallographically independent SiF62– dianions (Si atoms are located on the 3.2 and 6/m inversion centres, and one-twelfth of a methanol molecule (C atoms are situated on the 622 inversion centres, other atoms are disordered between general positions. In (I, all F atoms of 3.2-located SiF62– dianions participate in the formation of symmetry-equivalent contacts to the H atoms of imidazolium fragments, thus forming rod-type ensembles positioned on the -6 axes. These `pillar' rods are, in turn, F...H interlinked through SiF62– dianions disordered around the 6/m centres. The twelvefold disordered methanol molecules are appended to this array by O—H...F hydrogen bonds to the 6/m located SiF62– dianions. In terms of graph-set notation, the first and second level networks in (I are N1 = C22(7[3R44(14]D22(4 and N2 = D22(5 (C—H...O hydrogen bonds are not considered. After locating all symmetrically independent atoms in the cation and anions, there remained a strong (> 3 e Å−3 residual electron density peak located at the 622 inversion centre. Treatment of this pre-refined model with the SQUEEZE procedure in PLATON [Spek (2009. Acta Cryst. D65, 148–155] revealed two voids per unit cell, indicative of the presence of the solvent methanol molecule disordered about the 622 inversion centre.

  12. Incorporation of Hydrogen Bond Angle Dependency into the Generalized Solvation Free Energy Density Model.

    Science.gov (United States)

    Ma, Songling; Hwang, Sungbo; Lee, Sehan; Acree, William E; No, Kyoung Tai

    2018-04-23

    To describe the physically realistic solvation free energy surface of a molecule in a solvent, a generalized version of the solvation free energy density (G-SFED) calculation method has been developed. In the G-SFED model, the contribution from the hydrogen bond (HB) between a solute and a solvent to the solvation free energy was calculated as the product of the acidity of the donor and the basicity of the acceptor of an HB pair. The acidity and basicity parameters of a solute were derived using the summation of acidities and basicities of the respective acidic and basic functional groups of the solute, and that of the solvent was experimentally determined. Although the contribution of HBs to the solvation free energy could be evenly distributed to grid points on the surface of a molecule, the G-SFED model was still inadequate to describe the angle dependency of the HB of a solute with a polarizable continuum solvent. To overcome this shortcoming of the G-SFED model, the contribution of HBs was formulated using the geometric parameters of the grid points described in the HB coordinate system of the solute. We propose an HB angle dependency incorporated into the G-SFED model, i.e., the G-SFED-HB model, where the angular-dependent acidity and basicity densities are defined and parametrized with experimental data. The G-SFED-HB model was then applied to calculate the solvation free energies of organic molecules in water, various alcohols and ethers, and the log P values of diverse organic molecules, including peptides and a protein. Both the G-SFED model and the G-SFED-HB model reproduced the experimental solvation free energies with similar accuracy, whereas the distributions of the SFED on the molecular surface calculated by the G-SFED and G-SFED-HB models were quite different, especially for molecules having HB donors or acceptors. Since the angle dependency of HBs was included in the G-SFED-HB model, the SFED distribution of the G-SFED-HB model is well described

  13. Transmission and compression of an intense relativistic electron beam produced by a converging annular diode with return current feedback through the cathode. Pt. 2. The experiments

    International Nuclear Information System (INIS)

    Kelly, J.G.; Schuch, R.L.

    1976-02-01

    The complete results of the experiments with the converging annular diode within return current fedback through the cathode (Triax) are reported herein. The diode was designed to focus a relativistic high-current electron beam to a small focus. It did confirm the Triaxial theory detailed in Part I, and it did achieve a factor of 10 areal compression with 50% efficiency (which was below expectations). There were two principal reasons for this shortfall. First, the rapid diode plasma motion of 10 cm/μsec that was discovered necessitated the use of larger A-K gaps than expected and led to thicker beam sheets than are needed for good focusing. Second, the intrinsic angular spread of the electrons, even from the best cathode surfaces, introduced excessive angular momentum into the beam so that only a minor portion of the electrons could reach the axis. However, the yield of useful information about diode physics in general and about the influence of prepulse, the role of diode plasmas, the motion of energetic beams within conducting boundaries, diode emission properties, and diode diagnostic techniques in particle has had a significant and useful impact on the electron beam program at Sandia

  14. Phosphomolybdic acid and ferric iron as efficient electron mediators for coupling biomass pretreatment to produce bioethanol and electricity generation from wheat straw

    Science.gov (United States)

    Yi Ding; Bo Du; Xuebing Zhao; J.Y. Zhu; Dehua Liu

    2017-01-01

    Phosphomolybdic acid (PMo12) was used as an electron mediator and proton carrier to mediate biomass pretreatment for ethanol production and electricity generation from wheat straw. In the pretreatment, lignin was oxidized anaerobically by PMo12 with solubilization of a fraction of hemicelluloses, and the PMo12...

  15. A molecular dynamics study for the isomerization of Ar solvated (benzene){sub 2}-K{sup +} heteroclusters

    Energy Technology Data Exchange (ETDEWEB)

    Alberti, M. [CERQT, Departament de Quimica Fisica Parc Cientific, Universitat de Barcelona, Marti i Franques, 1, 08028 Barcelona (Spain); Pacifici, L. [Department of Mathematics and Computer Science, University of Perugia, via Vanvitelli, 1 06123 Perugia (Italy); Lagana, A. [Department of Chemistry, University of Perugia, via Elce di Sotto, 8 06123 Perugia (Italy)], E-mail: lag@dyn.unipg.it; Aguilar, A. [CERQT, Departament de Quimica Fisica Parc Cientific, Universitat de Barcelona, Marti i Franques, 1, 08028 Barcelona (Spain)

    2006-08-21

    A dynamical study of the (benzene){sub 2}-K{sup +} heteroclusters solvated by Ar atoms has been performed using an analytical force field of the atom (ion)-bond type. An analysis of the relevant calculated structural and energetic properties of these systems is made to understand involved molecular processes. The key effect found in the calculations is the tieing up of the two rings to sandwich K{sup +} and the weaking of this effect by solvation.

  16. Structural and computational study of 1,2,4-triazolin-5-thione derivative and its DMSO solvate

    Science.gov (United States)

    Dybała, Izabela; Wawrzycka-Gorczyca, Irena; Struga, Marta

    2017-11-01

    The solid state structure of 3-(4-phenyl-5-oxo-1,2,4-triazolin-1-ylmethyl)-4-cyclohexyl-1,2,4-triazolin-5-thione (1) was characterized by FT-IR and X-ray diffraction experiment. Additionally, molecular and crystal structure of its DMSO solvate (1DMSO) has been determined by X-ray diffraction method. The influence of DMSO molecules incorporation to the crystal lattice on geometry of triazolin-5-thione derivative molecule and crystal packing was analyzed. Non-covalent bonds within the crystals are additionally visualized by determination of Hirshfeld surfaces. According to results of conformational analysis in gas, molecule of triazolin-5-thione derivative adopts the lowest energy conformation in 1DMSO crystal. The crystal structure of 1 and 1DMSO were compared with previously described structurally similar compounds, in which the cyclohexyl substituent was replaced by aromatic one (phenyl/methoxyphenyl). Very interesting differences in molecules association were found by comparing the crystal structures of 1 and 1DMSO with their, mentioned above, aromatic derivatives. Interesting properties of triazolin-5-thione derivatives are connected with their π-electron delocalization effects, thus aromaticity of heterocyclic fragments has been investigated by means of the HOMA index. Comparison of aromaticity calculations results with association tendency of molecules shows that triazolin-5-one fragments reach higher aromaticity when nitrogen atom from this moiety acts as a donor in strong Nsbnd H⋯N hydrogen bonds.

  17. Coarse-grained models using local-density potentials optimized with the relative entropy: Application to implicit solvation

    International Nuclear Information System (INIS)

    Sanyal, Tanmoy; Shell, M. Scott

    2016-01-01

    Bottom-up multiscale techniques are frequently used to develop coarse-grained (CG) models for simulations at extended length and time scales but are often limited by a compromise between computational efficiency and accuracy. The conventional approach to CG nonbonded interactions uses pair potentials which, while computationally efficient, can neglect the inherently multibody contributions of the local environment of a site to its energy, due to degrees of freedom that were coarse-grained out. This effect often causes the CG potential to depend strongly on the overall system density, composition, or other properties, which limits its transferability to states other than the one at which it was parameterized. Here, we propose to incorporate multibody effects into CG potentials through additional nonbonded terms, beyond pair interactions, that depend in a mean-field manner on local densities of different atomic species. This approach is analogous to embedded atom and bond-order models that seek to capture multibody electronic effects in metallic systems. We show that the relative entropy coarse-graining framework offers a systematic route to parameterizing such local density potentials. We then characterize this approach in the development of implicit solvation strategies for interactions between model hydrophobes in an aqueous environment.

  18. Predicting cyclohexane/water distribution coefficients for the SAMPL5 challenge using MOSCED and the SMD solvation model

    Science.gov (United States)

    Diaz-Rodriguez, Sebastian; Bozada, Samantha M.; Phifer, Jeremy R.; Paluch, Andrew S.

    2016-11-01

    We present blind predictions using the solubility parameter based method MOSCED submitted for the SAMPL5 challenge on calculating cyclohexane/water distribution coefficients at 298 K. Reference data to parameterize MOSCED was generated with knowledge only of chemical structure by performing solvation free energy calculations using electronic structure calculations in the SMD continuum solvent. To maintain simplicity and use only a single method, we approximate the distribution coefficient with the partition coefficient of the neutral species. Over the final SAMPL5 set of 53 compounds, we achieved an average unsigned error of 2.2± 0.2 log units (ranking 15 out of 62 entries), the correlation coefficient ( R) was 0.6± 0.1 (ranking 35), and 72± 6 % of the predictions had the correct sign (ranking 30). While used here to predict cyclohexane/water distribution coefficients at 298 K, MOSCED is broadly applicable, allowing one to predict temperature dependent infinite dilution activity coefficients in any solvent for which parameters exist, and provides a means by which an excess Gibbs free energy model may be parameterized to predict composition dependent phase-equilibrium.

  19. Thermodynamics of sublimation and solvation for bicyclo-derivatives of 1,3-thiazine

    International Nuclear Information System (INIS)

    Ol’khovich, Marina V.; Blokhina, Svetlana V.; Sharapova, Angelica V.; Perlovich, German L.; Proshin, Alexey N.

    2013-01-01

    Highlights: • Temperature dependencies of saturated vapor pressure of new bicyclo-derivatives were obtained. • Thermodynamic functions of sublimation and solvation were calculated. • The correlations between thermodynamic functions and molecular descriptors are discussed. - Abstract: Temperature dependencies of saturated vapor pressure of novel bicyclo-derivatives of 1,3-thiazine with methoxy- and carbonyl-substituents have been obtained by method of transference by means of an inert gas carrier. Thermodynamic functions of sublimation have been calculated. Correlations between thermodynamic functions of sublimation and thermophysical properties of the substances and molecular descriptors have been established. The enthalpies of solvation of compounds were calculated using the measured values of enthalpies of sublimation and of standard enthalpies of solution in hexane and buffer

  20. Variation of the solvation number of Eu(III) in mixed system of methanol and water

    International Nuclear Information System (INIS)

    Suganuma, H.; Arisaka, M.; Omori, T.; Satoh, I.; Choppin, G.R.

    1999-01-01

    The stability constants (β 1 ) of the monofluoride complex of Eu(III) have been determined in mixed solvents of methanol and water at a 0.10 M ionic strength using a solvent extraction technique. The values of ln β 1 increase as the mole fraction of methanol in the mixed solvent system increases. The variation in the stability constants can be correlated with both the large effect due to the solvation of F and the small effect due to both (1) the solvation of cations in connection with complexation and (2) the electrostatic attraction between Eu 3+ and F - . Based on the variation in the sum of (1) and (2) in water and the mixed solvent solutions, it was determined that the coordination number (CN) of Eu(III) varied from a mixture of CN = 9 and 8 to CN = 8 at about a 0.03 mole fraction of methanol in the mixed solvent. (orig.)

  1. Quantitative prediction of solvation free energy in octanol of organic compounds.

    Science.gov (United States)

    Delgado, Eduardo J; Jaña, Gonzalo A

    2009-03-01

    The free energy of solvation, DeltaGS0, in octanol of organic compounds is quantitatively predicted from the molecular structure. The model, involving only three molecular descriptors, is obtained by multiple linear regression analysis from a data set of 147 compounds containing diverse organic functions, namely, halogenated and non-halogenated alkanes, alkenes, alkynes, aromatics, alcohols, aldehydes, ketones, amines, ethers and esters; covering a DeltaGS0 range from about -50 to 0 kJ.mol(-1). The model predicts the free energy of solvation with a squared correlation coefficient of 0.93 and a standard deviation, 2.4 kJ.mol(-1), just marginally larger than the generally accepted value of experimental uncertainty. The involved molecular descriptors have definite physical meaning corresponding to the different intermolecular interactions occurring in the bulk liquid phase. The model is validated with an external set of 36 compounds not included in the training set.

  2. Quantitative Prediction of Solvation Free Energy in Octanol of Organic Compounds

    Directory of Open Access Journals (Sweden)

    Eduardo J. Delgado

    2009-03-01

    Full Text Available The free energy of solvation, ΔGS0 , in octanol of organic compunds is quantitatively predicted from the molecular structure. The model, involving only three molecular descriptors, is obtained by multiple linear regression analysis from a data set of 147 compounds containing diverse organic functions, namely, halogenated and non-halogenated alkanes, alkenes, alkynes, aromatics, alcohols, aldehydes, ketones, amines, ethers and esters; covering a ΔGS0 range from about –50 to 0 kJ·mol-1. The model predicts the free energy of solvation with a squared correlation coefficient of 0.93 and a standard deviation, 2.4 kJ·mol-1, just marginally larger than the generally accepted value of experimental uncertainty. The involved molecular descriptors have definite physical meaning corresponding to the different intermolecular interactions occurring in the bulk liquid phase. The model is validated with an external set of 36 compounds not included in the training set.

  3. Sparingly Solvating Electrolytes for High Energy Density Lithium-Sulfur Batteries

    Energy Technology Data Exchange (ETDEWEB)

    Cheng, Lei; Curtiss, Larry A.; Zavadil, Kevin R.; Gewirth, Andrew A.; Shao, Yuyan; Gallagher, Kevin

    2016-07-11

    Moving to lighter and less expensive battery chemistries compared to lithium-ion requires the control of energy storage mechanisms based on chemical transformations rather than intercalation. Lithium sulfur (Li/S) has tremendous theoretical specific energy, but contemporary approaches to control this solution-mediated, precipitation-dissolution chemistry requires using large excesses of electrolyte to fully solubilize the polysulfide intermediate. Achieving reversible electrochemistry under lean electrolyte operation is the only path for Li/S to move beyond niche applications to potentially transformational performance. An emerging topic for Li/S research is the use of sparingly solvating electrolytes and the creation of design rules for discovering new electrolyte systems that fundamentally decouple electrolyte volume from reaction mechanism. This perspective presents an outlook for sparingly solvating electrolytes as the key path forward for longer-lived, high-energy density Li/S batteries including an overview of this promising new concept and some strategies for accomplishing it.

  4. A Series of Supramolecular Complexes for Solar Energy Conversion via Water Reduction to Produce Hydrogen: An Excited State Kinetic Analysis of Ru(II,Rh(III,Ru(II Photoinitiated Electron Collectors

    Directory of Open Access Journals (Sweden)

    Shamindri M. Arachchige

    2011-12-01

    Full Text Available Mixed-metal supramolecular complexes have been designed that photochemically absorb solar light, undergo photoinitiated electron collection and reduce water to produce hydrogen fuel using low energy visible light. This manuscript describes these systems with an analysis of the photophysics of a series of six supramolecular complexes, [{(TL2Ru(dpp}2RhX2](PF65 with TL = bpy, phen or Ph2phen with X = Cl or Br. The process of light conversion to a fuel requires a system to perform a number of complicated steps including the absorption of light, the generation of charge separation on a molecular level, the reduction by one and then two electrons and the interaction with the water substrate to produce hydrogen. The manuscript explores the rate of intramolecular electron transfer, rate of quenching of the supramolecules by the DMA electron donor, rate of reduction of the complex by DMA from the 3MLCT excited state, as well as overall rate of reduction of the complex via visible light excitation. Probing a series of complexes in detail exploring the variation of rates of important reactions as a function of sub-unit modification provides insight into the role of each process in the overall efficiency of water reduction to produce hydrogen. The kinetic analysis shows that the complexes display different rates of excited state reactions that vary with TL and halide. The role of the MLCT excited state is elucidated by this kinetic study which shows that the 3MLCT state and not the 3MMCT is likely that key contributor to the photoreduction of these complexes. The kinetic analysis of the excited state dynamics and reactions of the complexes are important as this class of supramolecules behaves as photoinitiated electron collectors and photocatalysts for the reduction of water to hydrogen.

  5. Influence of Doppler and 'Stark' effects on the shape of the autoionization peaks in electron energy spectra produced in ion-atom collisions

    International Nuclear Information System (INIS)

    Gleizes, A.; Benoit-Cattin, P.; Bordenave-Montesquieu, A.; Merchez, H.

    1976-01-01

    A detailed study is given of the influence of the Doppler shift and broadening on the spectra of electrons ejected by autoionization in collisions between heavy particles. General formulae have been obtained which permit the validity of results already published by other authors to be discussed. These results have been applied to the spectra of electrons ejected in He + -He collisions at 15 keV. The variation of the width of the autoionization peaks against ejection angle is well explained by Doppler broadening. On the contrary, the shape of these peaks cannot be due to the Doppler effect but rather to the Stark effect which is also studied in various experimental cases; it has been verified that the latter effect disappears in collisions between neutral particles for which symmetric peaks at 15 keV are obtained. (author)

  6. Heat Production by the Denitrifying Bacterium Pseudomonas fluorescens and the Dissimilatory Ammonium-Producing Bacterium Pseudomonas putrefaciens during Anaerobic Growth with Nitrate as the Electron Acceptor

    OpenAIRE

    Samuelsson, M.-O.; Cadez, P.; Gustafsson, L.

    1988-01-01

    The heat production rate and the simultaneous nitrate consumption and production and consumption of nitrite and nitrous oxide were monitored during the anaerobic growth of two types of dissimilatory nitrate reducers. Pseudomonas fluorescens, a denitrifier, consumed nitrate and accumulated small amounts of nitrite or nitrous oxide. The heat production rate increased steadily during the course of nitrate consumption and decreased rapidly concomitant with the depletion of the electron acceptors....

  7. Hybrid Perovskite Thin-Film Photovoltaics: In Situ Diagnostics and Importance of the Precursor Solvate Phases

    KAUST Repository

    Munir, Rahim

    2016-11-07

    Solution-processed hybrid perovskite semiconductors attract a great deal of attention, but little is known about their formation process. The one-step spin-coating process of perovskites is investigated in situ, revealing that thin-film formation is mediated by solid-state precursor solvates and their nature. The stability of these intermediate phases directly impacts the quality and reproducibility of thermally converted perovskite films and their photovoltaic performance.

  8. Solvation-based vapour pressure model for (solvent + salt) systems in conjunction with the Antoine equation

    International Nuclear Information System (INIS)

    Senol, Aynur

    2013-01-01

    Highlights: • Vapour pressures of (solvent + salt) systems have been estimated through a solvation-based model. • Two structural forms of the generalized solvation model using the Antoine equation have been performed. • A simplified concentration-dependent vapour pressure model has been also processed. • The model reliability analysis has been performed in terms of a log-ratio objective function. • The reliability of the models has been interpreted in terms of the statistical design factors. -- Abstract: This study deals with modelling the vapour pressure of a (solvent + salt) system on the basis of the principles of LSER. The solvation model framework clarifies the simultaneous impact of several physical variables such as the vapour pressure of a pure solvent estimated by the Antoine equation, the solubility and solvatochromic parameters of the solvent and the physical properties of the ionic salt. It has been analyzed independently the performance of two structural forms of the generalized model, i.e., a relation depending on an integration of the properties of the solvent and the ionic salt and a relation on a reduced property-basis. A simplified concentration-dependent vapour pressure model has been also explored and implemented on the relevant systems. The vapour pressure data of sixteen (solvent + salt) systems have been processed to analyze statistically the reliability of existing models in terms of a log–ratio objective function. The proposed vapour pressure models match relatively well the observed performance, yielding the overall design factors of 1.066 and 1.073 for the solvation-based models with the integrated and reduced properties, and 1.008 for the concentration-based model, respectively

  9. Solvation behavior of carbonate-based electrolytes in sodium ion batteries.

    Science.gov (United States)

    Cresce, Arthur V; Russell, Selena M; Borodin, Oleg; Allen, Joshua A; Schroeder, Marshall A; Dai, Michael; Peng, Jing; Gobet, Mallory P; Greenbaum, Steven G; Rogers, Reginald E; Xu, Kang

    2016-12-21

    Sodium ion batteries are on the cusp of being a commercially available technology. Compared to lithium ion batteries, sodium ion batteries can potentially offer an attractive dollar-per-kilowatt-hour value, though at the penalty of reduced energy density. As a materials system, sodium ion batteries present a unique opportunity to apply lessons learned in the study of electrolytes for lithium ion batteries; specifically, the behavior of the sodium ion in an organic carbonate solution and the relationship of ion solvation with electrode surface passivation. In this work the Li + and Na + -based solvates were characterized using electrospray mass spectrometry, infrared and Raman spectroscopy, 17 O, 23 Na and pulse field gradient double-stimulated-echo pulse sequence nuclear magnetic resonance (NMR), and conductivity measurements. Spectroscopic evidence demonstrate that the Li + and Na + cations share a number of similar ion-solvent interaction trends, such as a preference in the gas and liquid phase for a solvation shell rich in cyclic carbonates over linear carbonates and fluorinated carbonates. However, quite different IR spectra due to the PF 6 - anion interactions with the Na + and Li + cations were observed and were rationalized with the help of density functional theory (DFT) calculations that were also used to examine the relative free energies of solvates using cluster - continuum models. Ion-solvent distances for Na + were longer than Li + , and Na + had a greater tendency towards forming contact pairs compared to Li + in linear carbonate solvents. In tests of hard carbon Na-ion batteries, performance was not well correlated to Na + solvent preference, leading to the possibility that Na + solvent preference may play a reduced role in the passivation of anode surfaces and overall Na-ion battery performance.

  10. Hybrid Perovskite Thin-Film Photovoltaics: In Situ Diagnostics and Importance of the Precursor Solvate Phases

    KAUST Repository

    Munir, Rahim; Sheikh, Arif D.; Abdelsamie, Maged; Hu, Hanlin; Yu, Liyang; Zhao, Kui; Kim, Taesoo; El Tall, Omar; Li, Ruipeng; Smilgies, Detlef M.; Amassian, Aram

    2016-01-01

    Solution-processed hybrid perovskite semiconductors attract a great deal of attention, but little is known about their formation process. The one-step spin-coating process of perovskites is investigated in situ, revealing that thin-film formation is mediated by solid-state precursor solvates and their nature. The stability of these intermediate phases directly impacts the quality and reproducibility of thermally converted perovskite films and their photovoltaic performance.

  11. Solution thermodynamics and preferential solvation of sulfamethazine in (methanol + water) mixtures

    International Nuclear Information System (INIS)

    Delgado, Daniel R.; Almanza, Ovidio A.; Martínez, Fleming; Peña, María A.; Jouyban, Abolghasem; Acree, William E.

    2016-01-01

    Highlights: • Solubility of sulfamethazine (SMT) was measured in (methanol + water) mixtures. • SMT solubility was correlated with Jouyban–Acree model. • Gibbs energy, enthalpy, and entropy of dissolution of SMT were calculated. • Non-linear enthalpy–entropy relationship was observed for SMT. • Preferential solvation of SMT by methanol was analyzed by using the IKBI method. - Abstract: The solubility of sulfamethazine (SMT) in {methanol (1) + water (2)} co-solvent mixtures was determined at five different temperatures from (293.15 to 313.15) K. The sulfonamide exhibited its highest mole fraction solubility in pure methanol (δ 1 = 29.6 MPa 1/2 ) and its lowest mole fraction solubility in water (δ 2 = 47.8 MPa 1/2 ) at each of the five temperatures studied. The Jouyban–Acree model was used to correlate/predict the solubility values. The respective apparent thermodynamic functions Gibbs energy, enthalpy, and entropy of solution were obtained from the solubility data through the van’t Hoff and Gibbs equations. Apparent thermodynamic quantities of mixing were also calculated for this drug using values of the ideal solubility reported in the literature. A non-linear enthalpy–entropy relationship was noted for SMT in plots of both the enthalpy vs. Gibbs energy of mixing and the enthalpy vs. entropy of mixing. These plots suggest two different trends according to the slopes obtained when the composition of the mixtures changes. Accordingly, the mechanism for SMT transfer processes in water-rich mixtures from water to the mixture with 0.70 in mass fraction of methanol is entropy driven. Conversely, the mechanism is enthalpy driven in mixtures whenever the methanol composition exceeds 0.70 mol fraction. An inverse Kirkwood–Buff integral analysis of the preferential solvation of SMT indicated that the drug is preferentially solvated by water in water-rich mixtures but is preferentially solvated by methanol in methanol-rich mixtures.

  12. Electron Tree

    DEFF Research Database (Denmark)

    Appelt, Ane L; Rønde, Heidi S

    2013-01-01

    The photo shows a close-up of a Lichtenberg figure – popularly called an “electron tree” – produced in a cylinder of polymethyl methacrylate (PMMA). Electron trees are created by irradiating a suitable insulating material, in this case PMMA, with an intense high energy electron beam. Upon discharge......, during dielectric breakdown in the material, the electrons generate branching chains of fractures on leaving the PMMA, producing the tree pattern seen. To be able to create electron trees with a clinical linear accelerator, one needs to access the primary electron beam used for photon treatments. We...... appropriated a linac that was being decommissioned in our department and dismantled the head to circumvent the target and ion chambers. This is one of 24 electron trees produced before we had to stop the fun and allow the rest of the accelerator to be disassembled....

  13. Refined Dummy Atom Model of Mg(2+) by Simple Parameter Screening Strategy with Revised Experimental Solvation Free Energy.

    Science.gov (United States)

    Jiang, Yang; Zhang, Haiyang; Feng, Wei; Tan, Tianwei

    2015-12-28

    Metal ions play an important role in the catalysis of metalloenzymes. To investigate metalloenzymes via molecular modeling, a set of accurate force field parameters for metal ions is highly imperative. To extend its application range and improve the performance, the dummy atom model of metal ions was refined through a simple parameter screening strategy using the Mg(2+) ion as an example. Using the AMBER ff03 force field with the TIP3P model, the refined model accurately reproduced the experimental geometric and thermodynamic properties of Mg(2+). Compared with point charge models and previous dummy atom models, the refined dummy atom model yields an enhanced performance for producing reliable ATP/GTP-Mg(2+)-protein conformations in three metalloenzyme systems with single or double metal centers. Similar to other unbounded models, the refined model failed to reproduce the Mg-Mg distance and favored a monodentate binding of carboxylate groups, and these drawbacks needed to be considered with care. The outperformance of the refined model is mainly attributed to the use of a revised (more accurate) experimental solvation free energy and a suitable free energy correction protocol. This work provides a parameter screening strategy that can be readily applied to refine the dummy atom models for metal ions.

  14. The role of solvation in the binding selectivity of the L-type calcium channel.

    Science.gov (United States)

    Boda, Dezső; Henderson, Douglas; Gillespie, Dirk

    2013-08-07

    We present grand canonical Monte Carlo simulation results for a reduced model of the L-type calcium channel. While charged residues of the protein amino acids in the selectivity filter are treated explicitly, most of the degrees of freedom (including the rest of the protein and the solvent) are represented by their dielectric response, i.e., dielectric continua. The new aspect of this paper is that the dielectric coefficient in the channel is different from that in the baths. The ions entering the channel, thus, cross a dielectric boundary at the entrance of the channel. Simulating this case has been made possible by our recent methodological development [D. Boda, D. Henderson, B. Eisenberg, and D. Gillespie, J. Chem. Phys. 135, 064105 (2011)]. Our main focus is on the effect of solvation energy (represented by the Born energy) on monovalent vs. divalent ion selectivity in the channel. We find no significant change in selectivity by changing the dielectric coefficient in the channel because the larger solvation penalty is counterbalanced by the enhanced Coulomb attraction inside the channel as soon as we use the Born radii (fitted to experimental hydration energies) to compute the solvation penalty from the Born equation.

  15. Modifying Poisson equation for near-solute dielectric polarization and solvation free energy

    Energy Technology Data Exchange (ETDEWEB)

    Yang, Pei-Kun, E-mail: peikun@isu.edu.tw

    2016-06-15

    Highlights: • We modify the Poisson equation. • The dielectric polarization was calculated from the modified Poisson equation. • The solvation free energies of the solutes were calculated from the dielectric polarization. • The calculated solvation free energies were similar to those obtained from MD simulations. - Abstract: The dielectric polarization P is important for calculating the stability of protein conformation and the binding affinity of protein–protein/ligand interactions and for exploring the nonthermal effect of an external electric field on biomolecules. P was decomposed into the product of the electric dipole moment per molecule p; bulk solvent density N{sub bulk}; and relative solvent molecular density g. For a molecular solute, 4πr{sup 2}p(r) oscillates with the distance r to the solute, and g(r) has a large peak in the near-solute region, as observed in molecular dynamics (MD) simulations. Herein, the Poisson equation was modified for computing p based on the modified Gauss’s law of Maxwell’s equations, and the potential of the mean force was used for computing g. For one or two charged atoms in a water cluster, the solvation free energies of the solutes obtained by these equations were similar to those obtained from MD simulations.

  16. Ultrafast dynamics of solvation and charge transfer in a DNA-based biomaterial.

    Science.gov (United States)

    Choudhury, Susobhan; Batabyal, Subrata; Mondol, Tanumoy; Sao, Dilip; Lemmens, Peter; Pal, Samir Kumar

    2014-05-01

    Charge migration along DNA molecules is a key factor for DNA-based devices in optoelectronics and biotechnology. The association of a significant amount of water molecules in DNA-based materials for the intactness of the DNA structure and their dynamic role in the charge-transfer (CT) dynamics is less documented in contemporary literature. In the present study, we have used a genomic DNA-cetyltrimethyl ammonium chloride (CTMA) complex, a technological important biomaterial, and Hoechest 33258 (H258), a well-known DNA minor groove binder, as fluorogenic probe for the dynamic solvation studies. The CT dynamics of CdSe/ZnS quantum dots (QDs; 5.2 nm) embedded in the as-prepared and swollen biomaterial have also been studied and correlated with that of the timescale of solvation. We have extended our studies on the temperature-dependent CT dynamics of QDs in a nanoenvironment of an anionic, sodium bis(2-ethylhexyl)sulfosuccinate reverse micelle (AOT RMs), whereby the number of water molecules and their dynamics can be tuned in a controlled manner. A direct correlation of the dynamics of solvation and that of the CT in the nanoenvironments clearly suggests that the hydration barrier within the Arrhenius framework essentially dictates the charge-transfer dynamics. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Ejection of solvated ions from electrosprayed methanol/water nanodroplets studied by molecular dynamics simulations.

    Science.gov (United States)

    Ahadi, Elias; Konermann, Lars

    2011-06-22

    The ejection of solvated small ions from nanometer-sized droplets plays a central role during electrospray ionization (ESI). Molecular dynamics (MD) simulations can provide insights into the nanodroplet behavior. Earlier MD studies have largely focused on aqueous systems, whereas most practical ESI applications involve the use of organic cosolvents. We conduct simulations on mixed water/methanol droplets that carry excess NH(4)(+) ions. Methanol is found to compromise the H-bonding network, resulting in greatly increased rates of ion ejection and solvent evaporation. Considerable differences in the water and methanol escape rates cause time-dependent changes in droplet composition. Segregation occurs at low methanol concentration, such that layered droplets with a methanol-enriched periphery are formed. This phenomenon will enhance the partitioning of analyte molecules, with possible implications for their ESI efficiencies. Solvated ions are ejected from the tip of surface protrusions. Solvent bridging prior to ion secession is more extensive for methanol/water droplets than for purely aqueous systems. The ejection of solvated NH(4)(+) is visualized as diffusion-mediated escape from a metastable basin. The process involves thermally activated crossing of a ~30 kJ mol(-1) free energy barrier, in close agreement with the predictions of the classical ion evaporation model.

  18. Improvements to the APBS biomolecular solvation software suite: Improvements to the APBS Software Suite

    Energy Technology Data Exchange (ETDEWEB)

    Jurrus, Elizabeth [Pacific Northwest National Laboratory, Richland Washington; Engel, Dave [Pacific Northwest National Laboratory, Richland Washington; Star, Keith [Pacific Northwest National Laboratory, Richland Washington; Monson, Kyle [Pacific Northwest National Laboratory, Richland Washington; Brandi, Juan [Pacific Northwest National Laboratory, Richland Washington; Felberg, Lisa E. [University of California, Berkeley California; Brookes, David H. [University of California, Berkeley California; Wilson, Leighton [University of Michigan, Ann Arbor Michigan; Chen, Jiahui [Southern Methodist University, Dallas Texas; Liles, Karina [Pacific Northwest National Laboratory, Richland Washington; Chun, Minju [Pacific Northwest National Laboratory, Richland Washington; Li, Peter [Pacific Northwest National Laboratory, Richland Washington; Gohara, David W. [St. Louis University, St. Louis Missouri; Dolinsky, Todd [FoodLogiQ, Durham North Carolina; Konecny, Robert [University of California San Diego, San Diego California; Koes, David R. [University of Pittsburgh, Pittsburgh Pennsylvania; Nielsen, Jens Erik [Protein Engineering, Novozymes A/S, Copenhagen Denmark; Head-Gordon, Teresa [University of California, Berkeley California; Geng, Weihua [Southern Methodist University, Dallas Texas; Krasny, Robert [University of Michigan, Ann Arbor Michigan; Wei, Guo-Wei [Michigan State University, East Lansing Michigan; Holst, Michael J. [University of California San Diego, San Diego California; McCammon, J. Andrew [University of California San Diego, San Diego California; Baker, Nathan A. [Pacific Northwest National Laboratory, Richland Washington; Brown University, Providence Rhode Island

    2017-10-24

    The Adaptive Poisson-Boltzmann Solver (APBS) software was developed to solve the equations of continuum electrostatics for large biomolecular assemblages that has provided impact in the study of a broad range of chemical, biological, and biomedical applications. APBS addresses three key technology challenges for understanding solvation and electrostatics in biomedical applications: accurate and efficient models for biomolecular solvation and electrostatics, robust and scalable software for applying those theories to biomolecular systems, and mechanisms for sharing and analyzing biomolecular electrostatics data in the scientific community. To address new research applications and advancing computational capabilities, we have continually updated APBS and its suite of accompanying software since its release in 2001. In this manuscript, we discuss the models and capabilities that have recently been implemented within the APBS software package including: a Poisson-Boltzmann analytical and a semi-analytical solver, an optimized boundary element solver, a geometry-based geometric flow solvation model, a graph theory based algorithm for determining pKa values, and an improved web-based visualization tool for viewing electrostatics.

  19. High-dimensional neural network potentials for solvation: The case of protonated water clusters in helium

    Science.gov (United States)

    Schran, Christoph; Uhl, Felix; Behler, Jörg; Marx, Dominik

    2018-03-01

    The design of accurate helium-solute interaction potentials for the simulation of chemically complex molecules solvated in superfluid helium has long been a cumbersome task due to the rather weak but strongly anisotropic nature of the interactions. We show that this challenge can be met by using a combination of an effective pair potential for the He-He interactions and a flexible high-dimensional neural network potential (NNP) for describing the complex interaction between helium and the solute in a pairwise additive manner. This approach yields an excellent agreement with a mean absolute deviation as small as 0.04 kJ mol-1 for the interaction energy between helium and both hydronium and Zundel cations compared with coupled cluster reference calculations with an energetically converged basis set. The construction and improvement of the potential can be performed in a highly automated way, which opens the door for applications to a variety of reactive molecules to study the effect of solvation on the solute as well as the solute-induced structuring of the solvent. Furthermore, we show that this NNP approach yields very convincing agreement with the coupled cluster reference for properties like many-body spatial and radial distribution functions. This holds for the microsolvation of the protonated water monomer and dimer by a few helium atoms up to their solvation in bulk helium as obtained from path integral simulations at about 1 K.

  20. Effect of solvation on reactions of aluminium, gallium, indium, zinc and cadmium with azo compounds

    International Nuclear Information System (INIS)

    Savvin, S.B.

    1985-01-01

    Colour reactions have been examined between Al, Ga, In, Zn, Cd and reagents of a group of chromotropic acid 2.7-bisazo derivatives (Picramin B, Picramin M, Methanyl B, sulphonitrophenol M, sulphonitrophenol B) in organo-aqueous solutions containing acetone, propanol, DMFA, DMSO and acetic acid. Sensitive colour reactions occur in all the cases in aceton- or propanol-containing solutions: more sensitive than in water for Al, Ga, In; new reactions for Zn and Cd which are specific for organo-aqueous media and not observed in aqueous solutions. Sensitive reactions are observed only for Al and Ga in DMSO or DMFA solutions. Zn, Cd and In do not give colour reactions in such solutions. Differences in colour reactions for the elements in DMFA- and DMSO-containing media are connected with different solvation effects of the solvents on certain cations. Preferable solvation of some cations has been confirmed by infrared studies and is in agreement with the data reported on selective solvation

  1. Elucidating the Solvation Structure and Dynamics of Lithium Polysulfides Resulting from Competitive Salt and Solvent Interactions

    Energy Technology Data Exchange (ETDEWEB)

    Rajput, Nav Nidhi; Murugesan, Vijayakumar; Shin, Yongwoo; Han, Kee Sung; Lau, Kah Chun; Chen, Junzheng; Liu, Jun; Curtiss, Larry A.; Mueller, Karl T.; Persson, Kristin A.

    2017-04-10

    Fundamental molecular level understanding of functional properties of liquid solutions provides an important basis for designing optimized electrolytes for numerous applica-tions. In particular, exhaustive knowledge of solvation structure, stability and transport properties is critical for developing stable electrolytes for fast charging and high energy density next-generation energy storage systems. Here we report the correlation between solubility, solvation structure and translational dynamics of a lithium salt (Li-TFSI) and polysulfides species using well-benchmarked classical molecular dynamics simulations combined with nuclear magnetic resonance (NMR). It is observed that the polysulfide chain length has a significant effect on the ion-ion and ion-solvent interaction as well as on the diffusion coefficient of the ionic species in solution. In particular, extensive cluster formation is observed in lower order poly-sulfides (Sx2-; x≤4), whereas the longer polysulfides (Sx2-; x>4) show high solubility and slow dynamics in the solu-tion. It is observed that optimal solvent/salt ratio is essen-tial to control the solubility and conductivity as the addi-tion of Li salt increases the solubility but decreases the mo-bility of the ionic species. This work provides a coupled theoretical and experimental study of bulk solvation struc-ture and transport properties of multi-component electro-lyte systems, yielding design metrics for developing optimal electrolytes with improved stability and solubility.

  2. Component identification of electron transport chains in curdlan-producing Agrobacterium sp. ATCC 31749 and its genome-specific prediction using comparative genome and phylogenetic trees analysis.

    Science.gov (United States)

    Zhang, Hongtao; Setubal, Joao Carlos; Zhan, Xiaobei; Zheng, Zhiyong; Yu, Lijun; Wu, Jianrong; Chen, Dingqiang

    2011-06-01

    Agrobacterium sp. ATCC 31749 (formerly named Alcaligenes faecalis var. myxogenes) is a non-pathogenic aerobic soil bacterium used in large scale biotechnological production of curdlan. However, little is known about its genomic information. DNA partial sequence of electron transport chains (ETCs) protein genes were obtained in order to understand the components of ETC and genomic-specificity in Agrobacterium sp. ATCC 31749. Degenerate primers were designed according to ETC conserved sequences in other reported species. DNA partial sequences of ETC genes in Agrobacterium sp. ATCC 31749 were cloned by the PCR method using degenerate primers. Based on comparative genomic analysis, nine electron transport elements were ascertained, including NADH ubiquinone oxidoreductase, succinate dehydrogenase complex II, complex III, cytochrome c, ubiquinone biosynthesis protein ubiB, cytochrome d terminal oxidase, cytochrome bo terminal oxidase, cytochrome cbb (3)-type terminal oxidase and cytochrome caa (3)-type terminal oxidase. Similarity and phylogenetic analyses of these genes revealed that among fully sequenced Agrobacterium species, Agrobacterium sp. ATCC 31749 is closest to Agrobacterium tumefaciens C58. Based on these results a comprehensive ETC model for Agrobacterium sp. ATCC 31749 is proposed.

  3. Angular distribution measurements of photo-neutron yields produced by 2.0 GeV electrons incident on thick targets

    International Nuclear Information System (INIS)

    Lee, H. S.; Ban, S.; Sanami, T.; Takahashi, K.; Sato, T.; Shin, K.; Chung, C.

    2005-01-01

    A study of differential photo-neutron yields by irradiation with 2 GeV electrons has been carried out. In this extension of a previous study in which measurements were made at an angle of 90 deg. relative to incident electrons, the differential photo-neutron yield was obtained at two other angles, 48 deg. and 140 deg., to study its angular characteristics. Photo-neutron spectra were measured using a pulsed beam time-of-flight method and a BC418 plastic scintillator. The reliable range of neutron energy measurement was 8-250 MeV. The neutron spectra were measured for 10 Xo-thick Cu, Sn, W and Pb targets. The angular distribution characteristics, together with the previous results for 90 deg., are presented in the study. The experimental results are compared with Monte Carlo calculation results. The yields predicted by MCNPX 2.5 tend to underestimate the measured ones. The same trend holds for the comparison results using the EGS4 and PICA3 codes. (authors)

  4. Angular distribution measurements of photo-neutron yields produced by 2.0 GeV electrons incident on thick targets.

    Science.gov (United States)

    Lee, Hee-Seock; Ban, Syuichi; Sanami, Toshiya; Takahashi, Kazutoshi; Sato, Tatsuhiko; Shin, Kazuo; Chung, Chinwha

    2005-01-01

    A study of differential photo-neutron yields by irradiation with 2 GeV electrons has been carried out. In this extension of a previous study in which measurements were made at an angle of 90 degrees relative to incident electrons, the differential photo-neutron yield was obtained at two other angles, 48 degrees and 140 degrees, to study its angular characteristics. Photo-neutron spectra were measured using a pulsed beam time-of-flight method and a BC418 plastic scintillator. The reliable range of neutron energy measurement was 8-250 MeV. The neutron spectra were measured for 10 Xo-thick Cu, Sn, W and Pb targets. The angular distribution characteristics, together with the previous results for 90 degrees, are presented in the study. The experimental results are compared with Monte Carlo calculation results. The yields predicted by MCNPX 2.5 tend to underestimate the measured ones. The same trend holds for the comparison results using the EGS4 and PICA3 codes.

  5. Producing the radioelectric effect in solid dielectrics by bombardment with accelerated electrons. Obrazovaniye radioelektretnogo effekta v tverdykh dielektrikakh v rezul'tate oblucheniya ikh uskorennymi elektronami

    Energy Technology Data Exchange (ETDEWEB)

    Zavadovskaya, E K; Annenkov, Yu M; Boev, S G; Sigaev, G I

    1976-01-01

    A theoretical and experimental study was made concerning the kinetics of formation of electric moments in solid dielectrics bombarded with fast electrons in the atmosphere. The energy of bombarding electrons in the experiment ranged from 0.6 to 2.0 MeV, at an incident flux density ranging 1.10/sup -9/ to 5.10/sup -7/ A/cm/sup 2/. The specimens were actually grounded during bonbardment, owing to the high electrical conductivity of the ionized ambient gas, and the electric moments were equal to zero. The formation of electric moments occurred after cessation of the bombardment, because the density of the accumulated space charge had become redistributed. An examination was made of the redistribution of space-charge density due to the electrical conductivity of the dielectric, due to intrinsic charge carriers, and due to the release of charges stored in traps. Analytical relations derived for the kinetics of the electric moments give a qualitative description of the experimental results. 5 references.

  6. SAMPL4, a blind challenge for computational solvation free energies: the compounds considered

    Science.gov (United States)

    Guthrie, J. Peter

    2014-03-01

    For the fifth time I have provided a set of solvation energies (1 M gas to 1 M aqueous) for a SAMPL challenge. In this set there are 23 blind compounds and 30 supplementary compounds of related structure to one of the blind sets, but for which the solvation energy is readily available. The best current values of each compound are presented along with complete documentation of the experimental origins of the solvation energies. The calculations needed to go from reported data to solvation energies are presented, with particular attention to aspects which are new to this set. For some compounds the vapor pressures (VP) were reported for the liquid compound, which is solid at room temperature. To correct from VPsubcooled liquid to VPsublimation requires ΔSfusion, which is only known for mannitol. Estimated values were used for the others, all but one of which were benzene derivatives and expected to have very similar values. The final compound for which ΔSfusion was estimated was menthol, which melts at 42 °C so that modest errors in ΔSfusion will have little effect. It was also necessary to look into the effects of including estimated values of ΔCp on this correction. The approximate sizes of the effects of inclusion of ΔCp in the correction from VPsubcooled liquid to VPsublimation were estimated and it was noted that inclusion of ΔCp invariably makes ΔGS more positive. To extend the set of compounds for which the solvation energy could be calculated we explored the use of boiling point (b.p.) data from Reaxys/Beilstein as a substitute for studies of the VP as a function of temperature. B.p. data are not always reliable so it was necessary to develop a criterion for rejecting outliers. For two compounds (chlorinated guaiacols) it became clear that inclusion represented overreach; for each there were only two independent pressure, temperature points, which is too little for a trustworthy extrapolation. For a number of compounds the extrapolation from lowest

  7. Electron pairing in dilute liquid metal-metal halide solutions

    Energy Technology Data Exchange (ETDEWEB)

    Selloni, A.; Car, R.; Parrinello, M.; Carnevali, P.

    1987-09-10

    Spin density functional theory is used to describe the interaction between solvated electrons in KCl in the high dilution limit. In agreement with recent calculations based on the path integral method our results for antiparallel spin predict a strong tendency to form localized bielectronic complexes. At variance with numerical path integral, our method can efficiently treat the case of parallel spins. For this case we find that electrons repel each other and localize into separate F-center-like states.

  8. Study of radionuclides created by 181Ta(γ,xn yp) reactions for bremsstrahlung photons produced by 150-MeV electrons

    International Nuclear Information System (INIS)

    Miller, M.A.; Dickens, J.K.

    1991-12-01

    Ten radionuclides, including isomers, from 172 Ta to 180 Ta and 180m Hf were produced by photon interactions with a sample of elemental tantalum and measured by counting photons using a high-resolution detection system. Relative yields of these radionuclides were obtained. In addition, precision half lives were obtained for 175,176,180 Ta and 180m Hf. Those obtained for the three Ta isotopes agree with previously reported values. For 180m Hf, the present measurements resulted in a half life determination of 6.05±0.06 hr, or about 10% longer than the currently adopted value for this half life

  9. Electron microscope study of vacancy clusters produced by quenching in magnesium; Etude par microscopie electronique des amas de lacunes crees par trempe dans le magnesium

    Energy Technology Data Exchange (ETDEWEB)

    Levy, V; Espinasse, J; Mairy, C; Hillairet, J [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

    1969-07-01

    Vacancy clustering in quenched magnesium has been studied by transmission electron microscopy. The nature of the vacancy loops observed, seems to depend essentially on the impurity content of the metal; this effect can be attributed to a variation of the stacking fault energy of magnesium due to impurities. (authors) [French] On a etudie par microscopie electronique en transmission les defauts crees par trempe dans le magnesium. Un effet considerable des impuretes du metal sur la nature des boucles obtenues par condensation de lacunes a ete mis en evidence; cet effet semble s'expliquer de facon satisfaisante par un abaissement de l'energie de faute d'empilement du magnesium du aux impuretes. (auteur)

  10. Modeling of electron beams produced by linear accelerator installed at CNSTN / optimization study for the case of radiation sterilization of medical products and pharmaceutical

    International Nuclear Information System (INIS)

    Jellikh, Jihed

    2011-01-01

    The evolution of particle accelerators has led to the disposal of a very wide diversity of applications, such as the technique of treatment with Beta radiations. an electron accelerator has been installed at the National Center for nuclear Sciences and Technologies CNSTN) with the aim of controlling this technology, its development and its use in the areas of agriculture, industry, human health and scientific research. this project is committed for the study of the exploitation of this new facility in the field of radio-sterilization of medical, pharmaceuticals, cosmetics and laboratory products. A numerical tool has been then developed to simulate the radio processing and to simplify this process. Due to this option of dose distribution modeling inside a studied product, it's possible to estimate the best configuration for the accelerator parameter setting. It is a solution allowing to guarantee at once the conformity of the treatment of a product, as well as the reliability of the installation.

  11. Scanning electron microscopical examination of the impact of laser patterning on microscopic inhomogeneities of Cu(In,Ga)(Se,S)2 absorbers produced by rapid thermal processing

    International Nuclear Information System (INIS)

    Künecke, U.; Hölzing, A.; Jost, S.; Lechner, R.; Vogt, H.; Heiß, A.; Palm, J.; Hock, R.; Wellmann, P.

    2013-01-01

    Laser scribing of the Mo back electrode is commonly applied to define the cell structure of Cu(In,Ga)(Se,S) 2 (CIGSSe) thin film solar cells. The patterning process was performed on laboratory samples using ns and ps pulse length laser processes. After structuring, CIGSSe absorbers were processed by rapid thermal processing (RTP) of stacked elemental layer precursors. Microscopic inhomogeneities were investigated on different sample positions. For samples structured with ns pulse, the absorber morphology in the laser line vicinity is different as compared to the morphology in the unstructured cell area. Scanning electron microscopy and energy-dispersive X-ray spectroscopy show significant changes in the absorber grain size and chemical composition. Close to the laser line, the typically observed Ga accumulation on the back contact is less pronounced and more Ga is incorporated closer to the surface leading to a smaller grain size. The observed changes are attributed to partial damaging of a diffusion barrier between glass and Mo induced by the ns laser process, which allows diffusion of sodium from the glass substrate into the absorber during RTP. The enhanced Ga incorporation closer to the surface is an indication for the influence of sodium on the local phase development during RTP. The damages of the diffusion barrier can be effectively prevented by the application of a ps laser scribing process. CIGSSe absorbers processed on samples structured with ps pulse length do not show the described microscopic inhomogeneities around the laser line. - Highlights: ► Scanning electron microscopy on Cu(In,Ga)(Se,S) 2 solar cell absorbers ► Laser patterning with ns laser pulse damages the sodium diffusion barrier. ► Improved laser patterning with ps laser pulse leaves diffusion barrier intact. ► Additional sodium changes phase development during absorber formation. ► Gallium content is increased at surface and decreased at backside of absorber

  12. Pendant unit effect on electron tunneling in U-shaped molecules

    International Nuclear Information System (INIS)

    Liu Min; Chakrabarti, Subhasis; Waldeck, David H.; Oliver, Anna M.; Paddon-Row, Michael N.

    2006-01-01

    The electron transfer reactions of three U-shaped donor-bridge-acceptor molecules with different pendant groups have been studied in different solvents as a function of temperature. Analysis of the electron transfer kinetics in nonpolar and weakly polar solvents provides experimental reaction Gibbs energies that are used to parameterize a molecular solvation model. This solvation model is then used to predict energetic parameters in the electron transfer rate constant expression and allow the electronic coupling between the electron donor and electron acceptor groups to be determined from the rate data. The U-shaped molecules differ by alkylation of the aromatic pendant group, which lies in the 'line-of-sight' between the donor and acceptor groups. The findings show that the electronic coupling through the pendant group is similar for these molecules

  13. Ultra-fast electron capture by electrosterically-stabilized gold nanoparticles.

    Science.gov (United States)

    Ghandi, Khashayar; Findlater, Alexander D; Mahimwalla, Zahid; MacNeil, Connor S; Awoonor-Williams, Ernest; Zahariev, Federico; Gordon, Mark S

    2015-07-21

    Ultra-fast pre-solvated electron capture has been observed for aqueous solutions of room-temperature ionic liquid (RTIL) surface-stabilized gold nanoparticles (AuNPs; ∼9 nm). The extraordinarily large inverse temperature dependent rate constants (k(e)∼ 5 × 10(14) M(-1) s(-1)) measured for the capture of electrons in solution suggest electron capture by the AuNP surface that is on the timescale of, and therefore in competition with, electron solvation and electron-cation recombination reactions. The observed electron transfer rates challenge the conventional notion that radiation induced biological damage would be enhanced in the presence of AuNPs. On the contrary, AuNPs stabilized by non-covalently bonded ligands demonstrate the potential to quench radiation-induced electrons, indicating potential applications in fields ranging from radiation therapy to heterogeneous catalysis.

  14. Effects of thermal annealing on the radiation produced electron paramagnetic resonance spectra of bovine and equine tooth enamel: Fossil and modern

    International Nuclear Information System (INIS)

    Weeks, Robert A.; Bogard, James S.; Elam, J. Michael; Weinand, Daniel C.; Kramer, Andrew

    2003-01-01

    The concentration of stable radiation-induced paramagnetic states in fossil teeth can be used as a measure of sample age. Temperature excursions >100 deg. C, however, can cause the paramagnetic state clock to differ from the actual postmortem time. We have heated irradiated enamel from both fossilized bovid and modern equine (MEQ) teeth for 30 min in 50 deg. C increments from 100 to 300 deg. C, measuring the electron paramagnetic resonance (EPR) spectrum after each anneal, to investigate such effects. Samples were irradiated again after the last anneal, with doses of 300-1200 Gy from 60 Co photons, and measured. Two unirradiated MEQ samples were also annealed for 30 min at 300 deg. C, one in an evacuated EPR tube and the other in a tube open to the atmosphere, and subsequently irradiated. The data showed that hyperfine components attributed to the alanine radical were not detected in the irradiated MEQ sample until after the anneals. The spectrum of the MEQ sample heated in air and then irradiated was similar to that of the heat treated fossil sample. We conclude that the hyperfine components are due to sample heating to temperatures/times >100 deg. C/30 min and that similarities between fossil and MEQ spectra after the 300 deg. C/30 min MEQ anneal are also due to sample heating. We conclude that the presence of the hyperfine components in spectra of fossil tooth enamel indicate that such thermal events occurred either at the time of death, or during the postmortem history

  15. Level excitation cross sections of Si I fragments produced by 100 eV electron impact on SiH4

    International Nuclear Information System (INIS)

    Sato, T.; Kono, A.; Goto, T.

    1988-01-01

    The fluorescence decay Si I atomic lines after electron impact excitation of SiH 4 molecular gas was observed, and the level excitation cross sections (LECS) of Si I fragments were determined by separating the contribution from cascade transitions to line emissions. Observed transitions were 4s 1 P--3p 2 1 D, 4s 3 P--3p 2 3 P, 3d 1 P--3p 2 1 S, 3d 1 D--3p 2 1 D, 3d 1 F--3p 2 1 D, 3d 3 P--3p 2 3 P, and 3p 3 3 D--3p 2 3 P, for which the LECSs of the upper levels were determined at 100 eV excitation energy. The contribution of the direct excitations to these line emissions were found to range from 37% to 80%. Analysis of the 4s 1 P--3p 2 1 D decay curve also gave the LECSs of the cascading levels 4p 1 P, 4p 1 S, and 4p 1 D. Also obtained were some radiative lifetimes not reported before

  16. Octanol-Water Partition Coefficient from 3D-RISM-KH Molecular Theory of Solvation with Partial Molar Volume Correction.

    Science.gov (United States)

    Huang, WenJuan; Blinov, Nikolay; Kovalenko, Andriy

    2015-04-30

    The octanol-water partition coefficient is an important physical-chemical characteristic widely used to describe hydrophobic/hydrophilic properties of chemical compounds. The partition coefficient is related to the transfer free energy of a compound from water to octanol. Here, we introduce a new protocol for prediction of the partition coefficient based on the statistical-mechanical, 3D-RISM-KH molecular theory of solvation. It was shown recently that with the compound-solvent correlation functions obtained from the 3D-RISM-KH molecular theory of solvation, the free energy functional supplemented with the correction linearly related to the partial molar volume obtained from the Kirkwood-Buff/3D-RISM theory, also called the "universal correction" (UC), provides accurate prediction of the hydration free energy of small compounds, compared to explicit solvent molecular dynamics [ Palmer , D. S. ; J. Phys.: Condens. Matter 2010 , 22 , 492101 ]. Here we report that with the UC reparametrized accordingly this theory also provides an excellent agreement with the experimental data for the solvation free energy in nonpolar solvent (1-octanol) and so accurately predicts the octanol-water partition coefficient. The performance of the Kovalenko-Hirata (KH) and Gaussian fluctuation (GF) functionals of the solvation free energy, with and without UC, is tested on a large library of small compounds with diverse functional groups. The best agreement with the experimental data for octanol-water partition coefficients is obtained with the KH-UC solvation free energy functional.

  17. Additive scheme for calculation of solvation enthalpies of heterocyclic aromatic compounds. Sublimation/vaporization enthalpy at 298.15 K

    International Nuclear Information System (INIS)

    Solomonov, Boris N.; Nagrimanov, Ruslan N.; Mukhametzyanov, Timur A.

    2016-01-01

    Highlights: • Additivity scheme for solvation enthalpies estimation of heteroaromatic compounds was proposed. • Method for determination of vaporization/sublimation enthalpies directly at 298.15 K was developed. • Solution enthalpies of 25 heteroaromatic compounds were measured. • Vaporization/sublimation enthalpies of 44 heteroaromatic compounds were determined. • Obtained values are in good agreement with the results of conventional methods. - Abstract: Hereby we propose a method for determination of vaporization and sublimation enthalpies of heterocyclic and carbonyl-containing aromatic compounds at 298.15 K. According to this method vaporization and sublimation enthalpies at 298.15 K are determined based on enthalpies of solvation and solution. Solvation enthalpies of heteroatomatic and carbonyl-containing compounds are calculated using an additive scheme from the solvation enthalpy of closest aromatic hydrocarbon and contributions related to the exchange of CH-groups of hydrocarbon with corresponding substituent atoms or groups. Measured solution enthalpies together with calculated solvation enthalpies allowed to calculate corresponding vaporization and sublimation enthalpies at 298.15 K for a large number of heterocyclic and carbonyl-containing compounds. We have also found that in a number of cases instead of solution enthalpy in benzene at 298.15 K fusion enthalpy at the melting temperature can be used. Comparison between literature data and calculated vaporization and sublimation enthalpies demonstrates satisfactory performance of the proposed method.

  18. Additive scheme for calculation of solvation enthalpies of heterocyclic aromatic compounds. Sublimation/vaporization enthalpy at 298.15 K

    Energy Technology Data Exchange (ETDEWEB)

    Solomonov, Boris N., E-mail: boris.solomonov@kpfu.ru; Nagrimanov, Ruslan N.; Mukhametzyanov, Timur A.

    2016-06-10

    Highlights: • Additivity scheme for solvation enthalpies estimation of heteroaromatic compounds was proposed. • Method for determination of vaporization/sublimation enthalpies directly at 298.15 K was developed. • Solution enthalpies of 25 heteroaromatic compounds were measured. • Vaporization/sublimation enthalpies of 44 heteroaromatic compounds were determined. • Obtained values are in good agreement with the results of conventional methods. - Abstract: Hereby we propose a method for determination of vaporization and sublimation enthalpies of heterocyclic and carbonyl-containing aromatic compounds at 298.15 K. According to this method vaporization and sublimation enthalpies at 298.15 K are determined based on enthalpies of solvation and solution. Solvation enthalpies of heteroatomatic and carbonyl-containing compounds are calculated using an additive scheme from the solvation enthalpy of closest aromatic hydrocarbon and contributions related to the exchange of CH-groups of hydrocarbon with corresponding substituent atoms or groups. Measured solution enthalpies together with calculated solvation enthalpies allowed to calculate corresponding vaporization and sublimation enthalpies at 298.15 K for a large number of heterocyclic and carbonyl-containing compounds. We have also found that in a number of cases instead of solution enthalpy in benzene at 298.15 K fusion enthalpy at the melting temperature can be used. Comparison between literature data and calculated vaporization and sublimation enthalpies demonstrates satisfactory performance of the proposed method.

  19. Naked Gold Nanoparticles and hot Electrons in Water.

    Science.gov (United States)

    Ghandi, Khashayar; Wang, Furong; Landry, Cody; Mostafavi, Mehran

    2018-05-08

    The ionizing radiation in aqueous solutions of gold nanoparticles, stabilized by electrostatic non-covalent intermolecular forces and steric interactions, with antimicrobial compounds, are investigated with picosecond pulse radiolysis techniques. Upon pulse radiolysis of an aqueous solution containing very low concentrations of gold nanoparticles with naked surfaces available in water (not obstructed by chemical bonds), a change to Cerenkov spectrum over a large range of wavelengths are observed and pre-solvated electrons are captured by gold nanoparticles exclusively (not by ionic liquid surfactants used to stabilize the nanoparticles). The solvated electrons are also found to decay rapidly compared with the decay kinetics in water. These very fast reactions with electrons in water could provide an enhanced oxidizing zone around gold nanoparticles and this could be the reason for radio sensitizing behavior of gold nanoparticles in radiation therapy.

  20. 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

  1. Effects of thermal annealing on the radiation produced electron paramagnetic resonance spectra of bovine and equine tooth enamel: Fossil and modern

    Science.gov (United States)

    Weeks, Robert A.; Bogard, James S.; Elam, J. Michael; Weinand, Daniel C.; Kramer, Andrew

    2003-06-01

    The concentration of stable radiation-induced paramagnetic states in fossil teeth can be used as a measure of sample age. Temperature excursions >100 °C, however, can cause the paramagnetic state clock to differ from the actual postmortem time. We have heated irradiated enamel from both fossilized bovid and modern equine (MEQ) teeth for 30 min in 50 °C increments from 100 to 300 °C, measuring the electron paramagnetic resonance (EPR) spectrum after each anneal, to investigate such effects. Samples were irradiated again after the last anneal, with doses of 300-1200 Gy from 60Co photons, and measured. Two unirradiated MEQ samples were also annealed for 30 min at 300 °C, one in an evacuated EPR tube and the other in a tube open to the atmosphere, and subsequently irradiated. The data showed that hyperfine components attributed to the alanine radical were not detected in the irradiated MEQ sample until after the anneals. The spectrum of the MEQ sample heated in air and then irradiated was similar to that of the heat treated fossil sample. We conclude that the hyperfine components are due to sample heating to temperatures/times >100 °C/30 min and that similarities between fossil and MEQ spectra after the 300 °C/30 min MEQ anneal are also due to sample heating. We conclude that the presence of the hyperfine components in spectra of fossil tooth enamel indicate that such thermal events occurred either at the time of death, or during the postmortem history.

  2. Measurements of Laser Plasma Instability (LPI) and Electron Density/Temperature Profiles in Plasmas Produced by the Nike KrF Laser

    Science.gov (United States)

    Oh, Jaechul; Weaver, J. L.; Serlin, V.; Obenschain, S. P.

    2016-10-01

    We will present results of simultaneous measurements of LPI-driven light scattering and density/temperature profiles in CH plasmas produced by the Nike krypton fluoride laser (λ = 248 nm). The primary diagnostics for the LPI measurement are time-resolved spectrometers with absolute intensity calibration in spectral ranges relevant to the optical detection of stimulated Raman scattering or two plasmon decay. The spectrometers are capable of monitoring signal intensity relative to thermal background radiation from plasma providing a useful way to analyze LPI initiation. For further understanding of LPI processes, the recently implemented grid image refractometer (Nike-GIR)a is used to measure the coronal plasma profiles. In this experiment, Nike-GIR is equipped with a 5th harmonic probe laser (λ = 213 nm) in attempt to probe into a high density region over the previous peak density with λ = 263 nm probe light ( 4 ×1021 cm-3). The LPI behaviors will be discussed with the measured data sets. Work supported by DoE/NNSA.

  3. Study of the effect hydrogen binding in the solvation of alkaline earth cations with MeOH in nitromethane using 1 H NMR technique and determination of ionic solvation number

    CERN Document Server

    Alizadeh, N

    2001-01-01

    A proton NMR method for the study of the effect hydrogen binding and determination of solvation numbers of alkaline earth cations with methanol (MeOH) in in tromethane (NM) as diluent is described. The method is based on monitoring the resonance frequency of MeOH protons as a function of MeOH to metal ion mole ratio at constant metal ion concentration. the average solvation number of cation, n, at any MeOH/ metal ion mole ration was calculated from the NMR chemical shift-mole ration data and was plotted against the mole ration values. The solvation numbers of alkaline earth cations were obtained from the limiting values of the corresponding n, vs. mole ratio plots.

  4. Study of the effect hydrogen binding in the solvation of alkaline earth cations with MeOH in nitromethane using 1 H NMR technique and determination of ionic solvation number

    International Nuclear Information System (INIS)

    Alizadeh, N.

    2001-01-01

    A proton NMR method for the study of the effect hydrogen binding and determination of solvation numbers of alkaline earth cations with methanol (MeOH) in in tromethane (NM) as diluent is described. The method is based on monitoring the resonance frequency of MeOH protons as a function of MeOH to metal ion mole ratio at constant metal ion concentration. the average solvation number of cation, n, at any MeOH/ metal ion mole ration was calculated from the NMR chemical shift-mole ration data and was plotted against the mole ration values. The solvation numbers of alkaline earth cations were obtained from the limiting values of the corresponding n, vs. mole ratio plots

  5. Evidence for Reduced Hydrogen-Bond Cooperativity in Ionic Solvation Shells from Isotope-Dependent Dielectric Relaxation

    Science.gov (United States)

    Cota, Roberto; Ottosson, Niklas; Bakker, Huib J.; Woutersen, Sander

    2018-05-01

    We find that the reduction in dielectric response (depolarization) of water caused by solvated ions is different for H2O and D2O . This isotope dependence allows us to reliably determine the kinetic contribution to the depolarization, which is found to be significantly smaller than predicted by existing theory. The discrepancy can be explained from a reduced hydrogen-bond cooperativity in the solvation shell: we obtain quantitative agreement between theory and experiment by reducing the Kirkwood correlation factor of the solvating water from 2.7 (the bulk value) to ˜1.6 for NaCl and ˜1 (corresponding to completely uncorrelated motion of water molecules) for CsCl.

  6. Towards a stable ion-solvating polymer electrolyte for advanced alkaline water electrolysis

    DEFF Research Database (Denmark)

    Aili, David; Wright, Andrew G.; Kraglund, Mikkel Rykær

    2017-01-01

    Advanced alkaline water electrolysis using ion-solvating polymer membranes as electrolytes represents a new direction in the field of electrochemical hydrogen production. Polybenzimidazole membranes equilibrated in aqueous KOH combine the mechanical robustness and gas-tightness of a polymer...... stability in alkaline environments. The novel electrolytes are extensively characterized with respect to physicochemical and electrochemical properties and the chemical stability is assessed in 0-50 wt% aqueous KOH for more than 6 months at 88 degrees C. In water electrolysis tests using porous 3...

  7. Compound forming extractants, solvating solvents and inert solvents IUPAC chemical data series

    CERN Document Server

    Marcus, Y; Kertes, A S

    2013-01-01

    Equilibrium Constants of Liquid-Liquid Distribution Reactions, Part III: Compound Forming Extractants, Solvating Solvents, and Inert Solvents focuses on the compilation of equilibrium constants of various compounds, such as acids, ions, salts, and aqueous solutions. The manuscript presents tables that show the distribution reactions of carboxylic and sulfonic acid extractants and their dimerization and other reactions in the organic phase and extraction reactions of metal ions from aqueous solutions. The book also states that the inorganic anions in these solutions are irrelevant, since they d

  8. Effective interactions between nanoparticles: Creating temperature-independent solvation environments for self-assembly

    Energy Technology Data Exchange (ETDEWEB)

    Yadav, Hari O. S., E-mail: cyz108802@chemistry.iitd.ac.in, E-mail: hariyadav.iitd@gmail.com; Shrivastav, Gourav; Agarwal, Manish; Chakravarty, Charusita [Department of Chemistry, Indian Institute of Technology-Delhi, New Delhi 110016 (India)

    2016-06-28

    The extent to which solvent-mediated effective interactions between nanoparticles can be predicted based on structure and associated thermodynamic estimators for bulk solvents and for solvation of single and pairs of nanoparticles is studied here. As a test of the approach, we analyse the strategy for creating temperature-independent solvent environments using a series of homologous chain fluids as solvents, as suggested by an experimental paper [M. I. Bodnarchuk et al., J. Am. Chem. Soc. 132, 11967 (2010)]. Our conclusions are based on molecular dynamics simulations of Au{sub 140}(SC{sub 10}H{sub 21}){sub 62} nanoparticles in n-alkane solvents, specifically hexane, octane, decane and dodecane, using the TraPPE-UA potential to model the alkanes and alkylthiols. The 140-atom gold core of the nanocrystal is held rigid in a truncated octahedral geometry and the gold-thiolate interaction is modeled using a Morse potential. The experimental observation was that the structural and rheological properties of n-alkane solvents are constant over a temperature range determined by equivalent solvent vapour pressures. We show that this is a consequence of the fact that long chain alkane liquids behave to a good approximation as simple liquids formed by packing of monomeric methyl/methylene units. Over the corresponding temperature range (233–361 K), the solvation environment is approximately constant at the single and pair nanoparticle levels under good solvent conditions. However, quantitative variations of the order of 10%–20% do exist in various quantities, such as molar volume of solute at infinite dilution, entropy of solvation, and onset distance for soft repulsions. In the opposite limit of a poor solvent, represented by vacuum in this study, the effective interactions between nanoparticles are no longer temperature-independent with attractive interactions increasing by up to 50% on decreasing the temperature from 361 K to 290 K, accompanied by an increase in

  9. Protonic charge defect structures in floating water bridges observed as Zundel and Eigen solvation arrangements

    Science.gov (United States)

    Teschke, Omar; de Castro, Jose Roberto; Valente Filho, Juracyr Ferraz; Soares, David Mendez

    2017-10-01

    Protonic arrangements were detected in water bridge structures using confocal Raman microscopy, and the spectra show two formed structures. The measured Raman spectra were modified using the voltage applied to the bridge structure, which changed the proportion of these two species. Initially, for a 6.3 kV applied voltage, there was a measurable increase in the bridge current above the Ohmic contribution and the observed Raman spectrum of this new injected specie corresponded to the computed spectrum for the Zundel protonic arrangement. As the voltage further increases a contribution from the Eigen proton solvation specie is added to the measured spectrum.

  10. Ligand Conformational and Solvation/Desolvation Free Energy in Protein-Ligand Complex Formation

    Czech Academy of Sciences Publication Activity Database

    Kolář, Michal; Fanfrlík, Jindřich; Hobza, Pavel

    2011-01-01

    Roč. 115, č. 16 (2011), s. 4718-4724 ISSN 1520-6106 R&D Projects: GA MŠk LC512; GA ČR GAP208/11/0295 Grant - others:Korea Science and Engineering Foundation(KR) R32-2008-000-10180-0; European Science Fund(XE) CZ.1.05/2.1.00/03.0058 Institutional research plan: CEZ:AV0Z40550506 Keywords : solvation free energy * SMD * HIV protease inhibitors Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.696, year: 2011

  11. Organic solvation of intercalated cations in V/sub 2/O/sub 5/ xerogels

    International Nuclear Information System (INIS)

    Lemordant, D.; Bouhaouss, A.; Aldbert, P.; Baffier, N.

    1986-01-01

    V/sub 2/O/sub 5/ xerogels (V/sub 2/O/sub 5/, 1.6H/sub 2/O) undergo a topotactic reversible exchange reaction at room temperature in organic solvents containing monovalent alkali or divalent (Mn/sup 2+/) cations. Basal spacing are dependent on solvent type and charge-to-radius ratio of guest cations. From the interlayer distances, two solvation stages have been inferred, depending on the nature of the solvent and of the cation, except with Cs/sup +/ for which no intracrystalline swelling by organic solvents is observed

  12. The effect of solvation on the radiation damage rate constants for adenine

    DEFF Research Database (Denmark)

    Milhøj, Birgitte Olai; Sauer, Stephan P. A.

    2016-01-01

    in calculations of Gibbs free energies and reaction rates for the reaction between the OH radical and the DNA nucleobase adenine using Density Functional Theory at the ωB97X-D/6-311++G(2df,2pd) level with the Eckart tunneling correction. The solvent, water, has been included through either the implicit...... polarizable continuum model (PCM) or through explicit modelling of micro-solvation by a single water molecule at the site of reaction as well as the combination of both. Scrutiny of the thermodynamics and kinetics of the individual sub-reactions suggests that the qualitative differences introduced...

  13. An analysis of 3D solvation structure in biomolecules: application to coiled coil serine and bacteriorhodopsin.

    Science.gov (United States)

    Hirano, Kenji; Yokogawa, Daisuke; Sato, Hirofumi; Sakaki, Shigeyoshi

    2010-06-17

    Three-dimensional (3D) solvation structure around coiled coil serine (Coil-Ser) and inner 3D hydration structure in bacteriorhodopsin (bR) were studied using a recently developed method named multicenter molecular Ornstein-Zernike equation (MC-MOZ) theory. In addition, a procedure for analyzing the 3D solvent distribution was proposed. The method enables us to calculate the coordination number of solvent water as well as the strength of hydrogen bonding between the water molecule and the protein. The results for Coil-Ser and bR showed very good agreement with the experimental observations.

  14. Watching the Solvation of Atoms in Liquids One Solvent Molecule at a Time

    Science.gov (United States)

    Bragg, Arthur E.; Glover, William J.; Schwartz, Benjamin J.

    2010-06-01

    We use mixed quantum-classical molecular dynamics simulations and ultrafast transient hole-burning spectroscopy to build a molecular-level picture of the motions of solvent molecules around Na atoms in liquid tetrahydrofuran. We find that even at room temperature, the solvation of Na atoms occurs in discrete steps, with the number of solvent molecules nearest the atom changing one at a time. This explains why the rate of solvent relaxation differs for different initial nonequilibrium states, and reveals how the solvent helps determine the identity of atomic species in liquids.

  15. Lieb-Liniger-like model of quantum solvation in CO-4HeN clusters

    Science.gov (United States)

    Farrelly, D.; Iñarrea, M.; Lanchares, V.; Salas, J. P.

    2016-05-01

    Small 4He clusters doped with various molecules allow for the study of "quantum solvation" as a function of cluster size. A peculiarity of quantum solvation is that, as the number of 4He atoms is increased from N = 1, the solvent appears to decouple from the molecule which, in turn, appears to undergo free rotation. This is generally taken to signify the onset of "microscopic superfluidity." Currently, little is known about the quantum mechanics of the decoupling mechanism, mainly because the system is a quantum (N + 1)-body problem in three dimensions which makes computations difficult. Here, a one-dimensional model is studied in which the 4He atoms are confined to revolve on a ring and encircle a rotating CO molecule. The Lanczos algorithm is used to investigate the eigenvalue spectrum as the number of 4He atoms is varied. Substantial solvent decoupling is observed for as few as N = 5 4He atoms. Examination of the Hamiltonian matrix, which has an almost block diagonal structure, reveals increasingly weak inter-block (solvent-molecule) coupling as the number of 4He atoms is increased. In the absence of a dopant molecule the system is similar to a Lieb-Liniger (LL) gas and we find a relatively rapid transition to the LL limit as N is increased. In essence, the molecule initially—for very small N—provides a central, if relatively weak, attraction to organize the cluster; as more 4He atoms are added, the repulsive interactions between the identical bosons start to dominate as the solvation ring (shell) becomes more crowded which causes the molecule to start to decouple. For low N, the molecule pins the atoms in place relative to itself; as N increases the atom-atom repulsion starts to dominate the Hamiltonian and the molecule decouples. We conclude that, while the notion of superfluidity is a useful and correct description of the decoupling process, a molecular viewpoint provides complementary insights into the quantum mechanism of the transition from a molecular

  16. First crystal structures of pharmaceutical ibrutinib: systematic solvate screening and characterization

    Czech Academy of Sciences Publication Activity Database

    Zvoníček, V.; Skořepová, E.; Dušek, Michal; Babor, M.; Zvatora, P.; Šoós, M.

    2017-01-01

    Roč. 17, č. 6 (2017), s. 3116-3127 ISSN 1528-7483 R&D Projects: GA MŠk LO1603; GA ČR GA17-23196S EU Projects: European Commission(XE) CZ.2.16/3.1.00/24510 Institutional support: RVO:68378271 Keywords : Ibrutinib solvates * anticancer drug * Raman spectroscopy * powder X-ray diffraction * crystal structure Subject RIV: BM - Solid Matter Physics ; Magnetism OBOR OECD: Condensed matter physics (including formerly solid state physics, supercond.) Impact factor: 4.055, year: 2016

  17. Grid inhomogeneous solvation theory: hydration structure and thermodynamics of the miniature receptor cucurbit[7]uril.

    Science.gov (United States)

    Nguyen, Crystal N; Young, Tom Kurtzman; Gilson, Michael K

    2012-07-28

    The displacement of perturbed water upon binding is believed to play a critical role in the thermodynamics of biomolecular recognition, but it is nontrivial to unambiguously define and answer questions about this process. We address this issue by introducing grid inhomogeneous solvation theory (GIST), which discretizes the equations of inhomogeneous solvation theory (IST) onto a three-dimensional grid situated in the region of interest around a solute molecule or complex. Snapshots from explicit solvent simulations are used to estimate localized solvation entropies, energies, and free energies associated with the grid boxes, or voxels, and properly summing these thermodynamic quantities over voxels yields information about hydration thermodynamics. GIST thus provides a smoothly varying representation of water properties as a function of position, rather than focusing on hydration sites where solvent is present at high density. It therefore accounts for full or partial displacement of water from sites that are highly occupied by water, as well as for partly occupied and water-depleted regions around the solute. GIST can also provide a well-defined estimate of the solvation free energy and therefore enables a rigorous end-states analysis of binding. For example, one may not only use a first GIST calculation to project the thermodynamic consequences of displacing water from the surface of a receptor by a ligand, but also account, in a second GIST calculation, for the thermodynamics of subsequent solvent reorganization around the bound complex. In the present study, a first GIST analysis of the molecular host cucurbit[7]uril is found to yield a rich picture of hydration structure and thermodynamics in and around this miniature receptor. One of the most striking results is the observation of a toroidal region of high water density at the center of the host's nonpolar cavity. Despite its high density, the water in this toroidal region is disfavored energetically and

  18. Directly relating gas-phase cluster measurements to solution-phase hydrolysis, the absolute standard hydrogen electrode potential, and the absolute proton solvation energy.

    Science.gov (United States)

    Donald, William A; Leib, Ryan D; O'Brien, Jeremy T; Williams, Evan R

    2009-06-08

    Solution-phase, half-cell potentials are measured relative to other half-cell potentials, resulting in a thermochemical ladder that is anchored to the standard hydrogen electrode (SHE), which is assigned an arbitrary value of 0 V. A new method for measuring the absolute SHE potential is demonstrated in which gaseous nanodrops containing divalent alkaline-earth or transition-metal ions are reduced by thermally generated electrons. Energies for the reactions 1) M(H(2)O)(24)(2+)(g) + e(-)(g)-->M(H(2)O)(24)(+)(g) and 2) M(H(2)O)(24)(2+)(g) + e(-)(g)-->MOH(H(2)O)(23)(+)(g) + H(g) and the hydrogen atom affinities of MOH(H(2)O)(23)(+)(g) are obtained from the number of water molecules lost through each pathway. From these measurements on clusters containing nine different metal ions and known thermochemical values that include solution hydrolysis energies, an average absolute SHE potential of +4.29 V vs. e(-)(g) (standard deviation of 0.02 V) and a real proton solvation free energy of -265 kcal mol(-1) are obtained. With this method, the absolute SHE potential can be obtained from a one-electron reduction of nanodrops containing divalent ions that are not observed to undergo one-electron reduction in aqueous solution.

  19. Studies of the disruption prevention by ECRH at plasma current rise stage in limiter discharges/Possibility of an internal transport barrier producing under dominating electron transport in the T-10 tokamak

    International Nuclear Information System (INIS)

    Alikaev, V.V.; Borshegovskij, A.A.; Chistyakov, V.V.

    2001-01-01

    'Studies of the Disruption Prevention by ECRH at Plasma Current Rise Stage in Limiter Discharges' - Studies of disruption prevention by means of ECRH in T-10 at the plasma current rise phase in limiter discharges with circular plasma cross-section were performed. Reliable disruption prevention by ECRH at HF power (P HF ) min level equal to 20% of ohmic heating power P OH was demonstrated. m/n=2/1 mode MHD-activity developed before disruption (with characteristic time ∼ 120 ms) can be considered as disruption precursor and can be used in a feedback system. 'Possibility of an Internal Transport Barrier Producing under Dominating Electron Transport in the T-10 Tokamak' - The reversed shear experiments were carried out on T-10 at the HF power up to 1MW. The reversed shear in the core was produced by on-axis ECCD in direction opposite to the plasma current. There are no obvious signs of Internal Transport Barriers formation under condition when high-k turbulence determines the electron transport. (author)

  20. Interface of the polarizable continuum model of solvation with semi-empirical methods in the GAMESS program

    DEFF Research Database (Denmark)

    Svendsen, Casper Steinmann; Blædel, Kristoffer L.; Christensen, Anders Steen

    2013-01-01

    An interface between semi-empirical methods and the polarized continuum model (PCM) of solvation successfully implemented into GAMESS following the approach by Chudinov et al (Chem. Phys. 1992, 160, 41). The interface includes energy gradients and is parallelized. For large molecules such as ubiq......An interface between semi-empirical methods and the polarized continuum model (PCM) of solvation successfully implemented into GAMESS following the approach by Chudinov et al (Chem. Phys. 1992, 160, 41). The interface includes energy gradients and is parallelized. For large molecules...