Increasing ion and fusion yield in a dense plasma focus by combination of pre-ionization and heavy ion gas admixture

NASA Astrophysics Data System (ADS)

Farmanfarmaei, B.; Yousefi, H. R.; Salem, M. K.; Sari, A. H.

2018-04-01

The results of an experimental study of pre-ionization and heavy gas introduced into driven gas in a plasma focus device are reported. To achieve this purpose, we made use of two methods: first, the pre-ionization method by applying the shunt resistor and second, the admixture of heavy ions. We applied the different shunt resistors and found the optimum amount to be 200 MΩ at an optimum pressure of 0.5 Torr. Ion yield that was measured by array of Faraday cups and the energy of fast ions that was calculated by using the time-of-flight method were raised up to 22% and 45%, and the impurity caused by anode's erosion was reduced approximately by 67% in comparison to when there was no pre-ionization. Also, we have used the admixture of 5% argon ions with nitrogen (working gas) to improve the ion yield up to 45% in comparison with pure nitrogen. Finally, for the first time, we have utilized the combination of these methods together and have, consequently, reached the maximum ion yield and fusion yield. With this new method, ion yield raised up to 70% greater than that of the previous condition, i.e., without pre-ionization and heavy ion admixture.

Ratios of double to single ionization of He and Ne by strong 400-nm laser pulses using the quantitative rescattering theory

NASA Astrophysics Data System (ADS)

Chen, Zhangjin; Li, Xiaojin; Zatsarinny, Oleg; Bartschat, Klaus; Lin, C. D.

2018-01-01

We present numerical simulations of the ratio between double and single ionization of He and Ne by intense laser pulses at wavelengths of 390 and 400 nm, respectively. The yields of doubly charged ions due to nonsequential double ionization (NSDI) are obtained by employing the quantitative rescattering (QRS) model. In this model, the NSDI ionization probability is expressed as a product of the returning electron wave packet (RWP) and the total scattering cross sections for laser-free electron impact excitation and electron impact ionization of the parent ion. According to the QRS theory, the same RWP is also responsible for the emission of high-energy above-threshold ionization photoelectrons. To obtain absolute double-ionization yields, the RWP is generated by solving the time-dependent Schrödinger equation (TDSE) within a one-electron model. The same TDSE results can also be taken to obtain single-ionization yields. By using the TDSE results to calibrate single ionization and the RWP obtained from the strong-field approximation, we further simplify the calculation such that the nonuniform laser intensity distribution in the focused laser beam can be accounted for. In addition, laser-free electron impact excitation and ionization cross sections are calculated using the state-of-the-art many-electron R -matrix theory. The simulation results for double-to-single-ionization ratios are found to compare well with experimental data and support the validity of the nonsequential double-ionization mechanism for the covered intensity region.

First-principles investigations on ionization and thermal conductivity of polystyrene for inertial confinement fusion applications

DOE PAGES

Hu, S. X.; Collins, Lee A.; Goncharov, V. N.; ...

2016-04-14

Using quantum molecular-dynamics (QMD) methods based on the density functional theory, we have performed first-principles investigations on the ionization and thermal conductivity of polystyrene (CH) over a wide range of plasma conditions (ρ = 0.5 to 100 g/cm 3 and T = 15,625 to 500,000 K). The ionization data from orbital-free molecular-dynamics calculations have been fitted with a “Saha-type” model as a function of the CH plasma density and temperature, which exhibits the correct behaviors of continuum lowering and pressure ionization. The thermal conductivities (κ QMD) of CH, derived directly from the Kohn–Sham molecular-dynamics calculations, are then analytically fitted withmore » a generalized Coulomb logarithm [(lnΛ) QMD] over a wide range of plasma conditions. When compared with the traditional ionization and thermal conductivity models used in radiation–hydrodynamics codes for inertial confinement fusion simulations, the QMD results show a large difference in the low-temperature regime in which strong coupling and electron degeneracy play an essential role in determining plasma properties. Furthermore, hydrodynamic simulations of cryogenic deuterium–tritium targets with CH ablators on OMEGA and the National Ignition Facility using the QMD-derived ionization and thermal conductivity of CH have predicted –20% variation in target performance in terms of hot-spot pressure and neutron yield (gain) with respect to traditional model simulations.« less

Using Wannier functions to improve solid band gap predictions in density functional theory

DOE PAGES

Ma, Jie; Wang, Lin-Wang

2016-04-26

Enforcing a straight-line condition of the total energy upon removal/addition of fractional electrons on eigen states has been successfully applied to atoms and molecules for calculating ionization potentials and electron affinities, but fails for solids due to the extended nature of the eigen orbitals. Here we have extended the straight-line condition to the removal/addition of fractional electrons on Wannier functions constructed within the occupied/unoccupied subspaces. It removes the self-interaction energies of those Wannier functions, and yields accurate band gaps for solids compared to experiments. It does not have any adjustable parameters and the computational cost is at the DFT level.more » This method can also work for molecules, providing eigen energies in good agreement with experimental ionization potentials and electron affinities. Our approach can be viewed as an alternative approach of the standard LDA+U procedure.« less

Strong-field ionization of H{sub 2} from ultraviolet to near-infrared wavelengths: Photoelectron energy and angular identifications

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

Wilbois, Timo; Helm, Hanspeter

2011-11-15

Strong-field ionization of molecular hydrogen is studied at wavelengths ranging from 300 to 800 nm using pulses of 100-fs duration. We find that over this wide wavelength range, from nominally 4-photon to 11-photon ionization, resonance features dominate the ionization probability at intensities below 10{sup 14} W/cm{sup 2}. Photoelectron momentum maps recorded by an imaging spectrometer are analyzed to identify the wavelength-dependent ionization pathways in single ionization of molecular hydrogen. A number of models, some empirical, which are appropriate for a quantitative interpretation of the spectra and the ionization yield are introduced. A near-absolute comparison of measured ionization yields at 398more » nm is made with the predictions based on a numerical solution [Y. V. Vanne and A. Saenz, Phys. Rev. A 79, 023421 (2009)] of the time-dependent Schroedinger equation for two correlated electrons.« less

Watching electrons tunnel

NASA Astrophysics Data System (ADS)

Moser, Simon

2008-03-01

To get insight to time resolved inner atomic or molecular processes, laser pulses of few femtoseconds or even attoseconds are needed. These short light pulse techniques ask for broad frequency spectra, control of dispersion and control of phase. Hence, linear optics fails and nonlinear optics in high electromagnetic fields is needed to satisfy the amount of control that is needed. One recent application of attosecond laser pulses is time resolved visualization of tunnel ionization in atoms applied to high electromagnetic fields. Here, Ne atom electrons are excited by an extreme ultraviolet attosecond laser pulse. After a while, a few cycles nearly infrared femtosecond laser pulse is applied to the atom causing tunnel ionization. The ion yield distribution can be measured as function of the delay time between excitation and ionization and so deliver insight to the time resolved mechanisms.

High Useful Yield and Isotopic Analysis of Uranium by Resonance Ionization Mass Spectrometry

DOE PAGES

Savina, Michael R.; Isselhardt, Brett H.; Kucher, Andrew; ...

2017-05-09

Useful yields from resonance ionization mass spectrometry can be extremely high compared to other mass spectrometry techniques, but uranium analysis shows strong matrix effects arising from the tendency of uranium to form strongly bound oxide molecules that do not dissociate appreciably on energetic ion bombardment. Here, we demonstrate a useful yield of 24% for metallic uranium. Modeling the laser ionization and ion transmission processes shows that the high useful yield is attributable to a high ion fraction achieved by resonance ionization. We quantify the reduction of uranium oxide surface layers by Ar + and Ga + sputtering. The useful yieldmore » for uranium atoms from a uranium dioxide matrix is 0.4% and rises to 2% when the surface is in sputter equilibrium with the ion beam. The lower useful yield from the oxide is almost entirely due to uranium oxide molecules reducing the neutral atom content of the sputtered flux. We also demonstrate rapid isotopic analysis of solid uranium oxide at a precision of <0.5% relative standard deviation using relatively broadband lasers to mitigate spectroscopic fractionation.« less

High Useful Yield and Isotopic Analysis of Uranium by Resonance Ionization Mass Spectrometry

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

Savina, Michael R.; Isselhardt, Brett H.; Kucher, Andrew

Useful yields from resonance ionization mass spectrometry can be extremely high compared to other mass spectrometry techniques, but uranium analysis shows strong matrix effects arising from the tendency of uranium to form strongly bound oxide molecules that do not dissociate appreciably on energetic ion bombardment. Here, we demonstrate a useful yield of 24% for metallic uranium. Modeling the laser ionization and ion transmission processes shows that the high useful yield is attributable to a high ion fraction achieved by resonance ionization. We quantify the reduction of uranium oxide surface layers by Ar + and Ga + sputtering. The useful yieldmore » for uranium atoms from a uranium dioxide matrix is 0.4% and rises to 2% when the surface is in sputter equilibrium with the ion beam. The lower useful yield from the oxide is almost entirely due to uranium oxide molecules reducing the neutral atom content of the sputtered flux. We also demonstrate rapid isotopic analysis of solid uranium oxide at a precision of <0.5% relative standard deviation using relatively broadband lasers to mitigate spectroscopic fractionation.« less

Monoterpene oxidation in an oxidative flow reactor: SOA yields and the relationship between bulk gas-phase properties and organic aerosol growth

NASA Astrophysics Data System (ADS)

Friedman, B.; Link, M.; Farmer, D.

2016-12-01

We use an oxidative flow reactor (OFR) to determine the secondary organic aerosol (SOA) yields of five monoterpenes (alpha-pinene, beta-pinene, limonene, sabinene, and terpinolene) at a range of OH exposures. These OH exposures correspond to aging timescales of a few hours to seven days. We further determine how SOA yields of beta-pinene and alpha-pinene vary as a function of seed particle type (organic vs. inorganic) and seed particle mass concentration. We hypothesize that the monoterpene structure largely accounts for the observed variance in SOA yields for the different monoterpenes. We also use high-resolution time-of-flight chemical ionization mass spectrometry to calculate the bulk gas-phase properties (O:C and H:C) of the monoterpene oxidation systems as a function of oxidant concentrations. Bulk gas-phase properties can be compared to the SOA yields to assess the capability of the precursor gas-phase species to inform the SOA yields of each monoterpene oxidation system. We find that the extent of oxygenated precursor gas-phase species corresponds to SOA yield.

Quantitative ionization chamber alignment to a water surface: Theory and simulation.

PubMed

Siebers, Jeffrey V; Ververs, James D; Tessier, Frédéric

2017-07-01

To examine the response properties of cylindrical cavity ionization chambers (ICs) in the depth-ionization buildup region so as to obtain a robust chamber-signal - based method for definitive water surface identification, hence absolute ionization chamber depth localization. An analytical model with simplistic physics and geometry is developed to explore the theoretical aspects of ionization chamber response near a phantom water surface. Monte Carlo simulations with full physics and ionization chamber geometry are utilized to extend the model's findings to realistic ion chambers in realistic beams and to study the effects of IC design parameters on the entrance dose response. Design parameters studied include full and simplified IC designs with varying central electrode thickness, wall thickness, and outer chamber radius. Piecewise continuous fits to the depth-ionization signal gradient are used to quantify potential deviation of the gradient discontinuity from the chamber outer radius. Exponential, power, and hyperbolic sine functional forms are used to model the gradient for chamber depths of zero to the depth of the gradient discontinuity. The depth-ionization gradient as a function of depth is maximized and discontinuous when a submerged IC's outer radius coincides with the water surface. We term this depth the gradient chamber alignment point (gCAP). The maximum deviation between the gCAP location and the chamber outer radius is 0.13 mm for a hypothetical 4 mm thick wall, 6.45 mm outer radius chamber using the power function fit, however, the chamber outer radius is within the 95% confidence interval of the gCAP determined by this fit. gCAP dependence on the chamber wall thickness is possible, but not at a clinically relevant level. The depth-ionization gradient has a discontinuity and is maximized when the outer-radius of a submerged IC coincides with the water surface. This feature can be used to auto-align ICs to the water surface at the time of scanning and/or be applied retrospectively to scan data to quantify absolute IC depth. Utilization of the gCAP should yield accurate and reproducible depth calibration for clinical depth-ionization measurements between setups and between users. © 2017 American Association of Physicists in Medicine.

Photoionization Modeling and the K Lines of Iron

NASA Technical Reports Server (NTRS)

Kallman, T. R.; Palmeri, P.; Bautista, M. A.; Mendoza, C.; Krolik, J. H.

2004-01-01

We calculate the efficiency of iron K line emission and iron K absorption in photoionized models using a new set of atomic data. These data are more comprehensive than those previously applied to the modeling of iron K lines from photoionized gases, and allow us to systematically examine the behavior of the properties of line emission and absorption as a function of the ionization parameter, density and column density of model constant density clouds. We show that, for example, the net fluorescence yield for the highly charged ions is sensitive to the level population distribution produced by photoionization, and these yields are generally smaller than those predicted assuming the population is according to statistical weight. We demonstrate that the effects of the many strongly damped resonances below the K ionization thresholds conspire to smear the edge, thereby potentially affecting the astrophysical interpretation of absorption features in the 7-9 keV energy band. We show that the centroid of the ensemble of K(alpha) lines, the K(beta) energy, and the ratio of the K(alpha(sub 1)) to K(alpha(sub 2)) components are all diagnostics of the ionization parameter of our model slabs.

Optical field ionization of atoms and ions using ultrashort laser pulses

NASA Astrophysics Data System (ADS)

Fittinghoff, D. N.

1993-12-01

This dissertation research is an investigation of the strong optical field ionization of atoms and ions by 120-fs, 614-run laser pulses and 130-fs, 800-nm laser pulses. The experiments have shown ionization that is enhanced above the predictions of sequential tunneling models for He(+2), Ne(+2), and Ar(+2). The ion yields for He(+1), Ne(sup +1) and Ar(sup +1) agree well with the theoretical predictions of optical tunneling models. Investigation of the polarization dependence of the ionization indicates that the enhancements are consistent with a nonsequential ionization mechanism in which the linearly polarized field drives the electron wavefunction back toward the ion core and causes double ionization through inelastic e-2e scattering. These investigations have initiated a number of other studies by other groups and are of current scientific interest in the fields of high-irradiance laser-matter interactions and production of high-density plasmas. This work involved the following: (1) Understanding the characteristic nature of the ion yields produced by tunneling ionization through investigation of analytic solutions for tunneling at optical frequencies. (2) Extensive characterization of the pulses produced by 614-nm and 800-ran ultrashort pulse lasers. Absolute calibration of the irradiance scale produced shows the practicality of the inverse problem--measuring peak laser irradiance using ion yields. (3) Measuring the ion yields for three noble gases using linear, circular and elliptical polarizations of laser pulses at 614-nm and 800-nm. The measurements are some of the first measurements for pulse widths as low as 120-fs.

Extreme ionization of Xe clusters driven by ultraintense laser fields

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

Heidenreich, Andreas; Last, Isidore; Jortner, Joshua

We applied theoretical models and molecular dynamics simulations to explore extreme multielectron ionization in Xe{sub n} clusters (n=2-2171, initial cluster radius R{sub 0}=2.16-31.0 A ring ) driven by ultraintense infrared Gaussian laser fields (peak intensity I{sub M}=10{sup 15}-10{sup 20} W cm{sup -2}, temporal pulse length {tau}=10-100 fs, and frequency {nu}=0.35 fs{sup -1}). Cluster compound ionization was described by three processes of inner ionization, nanoplasma formation, and outer ionization. Inner ionization gives rise to high ionization levels (with the formation of (Xe{sup q+}){sub n} with q=2-36), which are amenable to experimental observation. The cluster size and laser intensity dependence of themore » inner ionization levels are induced by a superposition of barrier suppression ionization (BSI) and electron impact ionization (EII). The BSI was induced by a composite field involving the laser field and an inner field of the ions and electrons, which manifests ignition enhancement and screening retardation effects. EII was treated using experimental cross sections, with a proper account of sequential impact ionization. At the highest intensities (I{sub M}=10{sup 18}-10{sup 20} W cm{sup -2}) inner ionization is dominated by BSI. At lower intensities (I{sub M}=10{sup 15}-10{sup 16} W cm{sup -2}), where the nanoplasma is persistent, the EII contribution to the inner ionization yield is substantial. It increases with increasing the cluster size, exerts a marked effect on the increase of the (Xe{sup q+}){sub n} ionization level, is most pronounced in the cluster center, and manifests a marked increase with increasing the pulse length (i.e., becoming the dominant ionization channel (56%) for Xe{sub 2171} at {tau}=100 fs). The EII yield and the ionization level enhancement decrease with increasing the laser intensity. The pulse length dependence of the EII yield at I{sub M}=10{sup 15}-10{sup 16} W cm{sup -2} establishes an ultraintense laser pulse length control mechanism of extreme ionization products.« less

Scattering of hydrogen, nitrogen and water ions from micro pore optic plates for application in spaceborne plasma instrumentation

NASA Astrophysics Data System (ADS)

Stude, Joan; Wieser, Martin; Barabash, Stas

2016-10-01

Time-of-flight mass spectrometers for upcoming space missions into enhanced radiation environments need to be small, light weight and energy efficient. Time-of-flight systems using surface interactions as start-event generation can be smaller than foil-type instruments. Start surfaces for such applications need to provide narrow angular scattering, high ionization yields and high secondary electron emissions to be effective. We measured the angular scattering, energy distribution and positive ionization yield of micro pore optics for incident hydrogen, nitrogen and water ions at 2 keV. Positive ionization yields of 2% for H+ , 0.5% for N+ and 0.2% for H2O+ were detected.

Watching the Real-time Evolution of a Laser Modified Atom Using Attosecond Pulses

NASA Astrophysics Data System (ADS)

Shivaram, Niranjan; Timmers, Henry; Tong, Xiao-Min; Sandhu, Arvinder

2011-10-01

In the presence of even moderately strong laser fields, atomic states are heavily modified and develop rich structure. Such a laser dressed atom can be described using the Floquet theory in which the laser dressed states called Floquet states are composed of different Fourier components. In this work we use XUV attosecond pulses to excite a He atom from its ground state to near-infrared (NIR) laser dressed Floquet states, which are ionized by the dressing laser field. Quantum interferences between Fourier components of these Floquet states lead to oscillations in He ion yield as a function of time-delay between the XUV and NIR pulses. From the ion yield signal we measure the quantum phase difference between transition matrix elements to two different Fourier components as a function of both time-delay (instantaneous NIR intensity) and NIR pulse peak intensity. These measurements along with information from time-dependent Schrodinger equation simulations enable us to observe the real-time evolution of the laser modified atom as the dominant Floquet state mediating the ionization changes from the 5p Floquet state to the 2p Floquet state with increasing NIR intensity.

Carrier-envelope phase-dependent ionization of Xe in intense, ultrafast (two-cycle) laser fields

NASA Astrophysics Data System (ADS)

Vasa, Parinda; Dharmadhikari, Aditya K.; Mathur, Deepak

2018-01-01

We report an experimental study that shows the dependence of the tunnel ionization of Xe by two-cycle, intense, near infrared light on the carrier-envelope-phase (CEP) of incident laser pulses. At low values of the optical field (E), the ionization yield is found to be maximum for cos-like pulses; the CEP dependence of the ion yield becomes stronger for higher charge states. At higher E-values, the CEP dependence either washes out or flips. A simple phenomenological model is used to confirm that our results fall within the ambit of the current understanding of ionization dynamics in strong, ultrashort optical fields. In the observed tunnel ionization of Xe, CEP effects appear to persist for longer, eight-cycle, pulses. Electron rescattering is observed to play a relatively unimportant role in the observed CEP dependence. These results provide fresh perspectives in the ionization mechanisms of multielectron systems in the few-cycle regime.

First-principles investigations on ionization and thermal conductivity of polystyrene for inertial confinement fusion applications

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

Hu, S. X., E-mail: shu@lle.rochester.edu; Goncharov, V. N.; McCrory, R. L.

2016-04-15

Using quantum molecular-dynamics (QMD) methods based on the density functional theory, we have performed first-principles investigations of the ionization and thermal conductivity of polystyrene (CH) over a wide range of plasma conditions (ρ = 0.5 to 100 g/cm{sup 3} and T = 15 625 to 500 000 K). The ionization data from orbital-free molecular-dynamics calculations have been fitted with a “Saha-type” model as a function of the CH plasma density and temperature, which gives an increasing ionization as the CH density increases even at low temperatures (T < 50 eV). The orbital-free molecular dynamics method is only used to gauge the average ionization behavior of CH under the average-atommore » model in conjunction with the pressure-matching mixing rule. The thermal conductivities (κ{sub QMD}) of CH, derived directly from the Kohn–Sham molecular-dynamics calculations, are then analytically fitted with a generalized Coulomb logarithm [(lnΛ){sub QMD}] over a wide range of plasma conditions. When compared with the traditional ionization and thermal conductivity models used in radiation–hydrodynamics codes for inertial confinement fusion simulations, the QMD results show a large difference in the low-temperature regime in which strong coupling and electron degeneracy play an essential role in determining plasma properties. Hydrodynamic simulations of cryogenic deuterium–tritium targets with CH ablators on OMEGA and the National Ignition Facility using the QMD-derived ionization and thermal conductivity of CH have predicted ∼20% variation in target performance in terms of hot-spot pressure and neutron yield (gain) with respect to traditional model simulations.« less

Calculations of the Electron Energy Distribution Function in a Uranium Plasma by Analytic and Monte Carlo Techniques. Ph.D. Thesis

NASA Technical Reports Server (NTRS)

Bathke, C. G.

1976-01-01

Electron energy distribution functions were calculated in a U235 plasma at 1 atmosphere for various plasma temperatures and neutron fluxes. The distributions are assumed to be a summation of a high energy tail and a Maxwellian distribution. The sources of energetic electrons considered are the fission-fragment induced ionization of uranium and the electron induced ionization of uranium. The calculation of the high energy tail is reduced to an electron slowing down calculation, from the most energetic source to the energy where the electron is assumed to be incorporated into the Maxwellian distribution. The pertinent collisional processes are electron-electron scattering and electron induced ionization and excitation of uranium. Two distinct methods were employed in the calculation of the distributions. One method is based upon the assumption of continuous slowing and yields a distribution inversely proportional to the stopping power. An iteration scheme is utilized to include the secondary electron avalanche. In the other method, a governing equation is derived without assuming continuous electron slowing. This equation is solved by a Monte Carlo technique.

Experimental investigation of the ionization mechanisms of uranium in thermal ionization mass spectrometry in the presence of carbon

NASA Astrophysics Data System (ADS)

Kraiem, M.; Mayer, K.; Gouder, T.; Seibert, A.; Wiss, T.; Thiele, H.; Hiernaut, J.-P.

2010-01-01

Thermal ionization mass spectrometry (TIMS) is a well established instrumental technique for providing accurate and precise isotope ratio measurements of elements with reasonably low first ionization potential. In nuclear safeguards and in environmental research, it is often required to measure the isotope ratios in small samples of uranium. Empirical studies had shown that the ionization yield of uranium and plutonium in a TIMS ion source can be significantly increased in the presence of a carbon source. But, even though carbon appeared crucial in providing high ionization yields, processes taking place on the ionization surface were still not well understood. This paper describes the experimental results obtained from an extended study on the evaporation and ionization mechanisms of uranium occurring on a rhenium mass spectrometry filament in the presence of carbon. Solid state reactions were investigated using X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). Additionally, vaporization measurements were performed with a modified-Knudsen cell mass spectrometer for providing information on the neutral uranium species in the vapor phase. Upon heating, under vacuum, the uranyl nitrate sample was found to turn into a uranium carbide compound, independent of the type of carbon used as ionization enhancer. With further heating, uranium carbide leads to formation of single charged uranium metal ions and a small amount of uranium carbide ions. The results are relevant for a thorough understanding of the ion source chemistry of a uranyl nitrate sample under reducing conditions. The significant increase in ionization yield described by many authors on the basis of empirical results can be now fully explained and understood.

Development of a Computationally Efficient, High Fidelity, Finite Element Based Hall Thruster Model

NASA Technical Reports Server (NTRS)

Jacobson, David (Technical Monitor); Roy, Subrata

2004-01-01

This report documents the development of a two dimensional finite element based numerical model for efficient characterization of the Hall thruster plasma dynamics in the framework of multi-fluid model. Effect of the ionization and the recombination has been included in the present model. Based on the experimental data, a third order polynomial in electron temperature is used to calculate the ionization rate. The neutral dynamics is included only through the neutral continuity equation in the presence of a uniform neutral flow. The electrons are modeled as magnetized and hot, whereas ions are assumed magnetized and cold. The dynamics of Hall thruster is also investigated in the presence of plasma-wall interaction. The plasma-wall interaction is a function of wall potential, which in turn is determined by the secondary electron emission and sputtering yield. The effect of secondary electron emission and sputter yield has been considered simultaneously, Simulation results are interpreted in the light of experimental observations and available numerical solutions in the literature.

Measuring the dependence of the decay curve on the electron energy deposit in NaI(Tl)

NASA Astrophysics Data System (ADS)

Choong, W.-S.; Bizarri, G.; Cherepy, N. J.; Hull, G.; Moses, W. W.; Payne, S. A.

2011-08-01

We report on the first measurement of the decay times of NaI(Tl) as a function of the deposited electron energy. It has been suggested that the decay curve depends on the ionization density, which is correlated with the electron energy deposit in the scintillator. The ionization creates excitation states, which can decay radiatively and non-radiatively through a number of competing processes. As a result, the rate at which the excitation decays depends on the ionization density. A measurement of the decay curve as a function of the ionization density will allow us to probe the kinetic rates of the competing processes. The Scintillator Light Yield Non-proportionality Characterization Instrument (SLYNCI) measures the electron response of scintillators utilizing fast sampling ADCs to digitize the raw signals from the detectors, and so can provide a measurement of the light pulse shape from the scintillator. Using data collected with the SLYNCI instrument, the intrinsic scintillation profile is extracted on an event-by-event basis by deconvolving the raw signal with the impulse response of the system. Scintillation profiles with the same electron energy deposit are summed to obtain decay curves as a function of the deposited electron energy. The decay time constants are obtained by fitting the decay curves with a two-component exponential decay. While a slight dependence of the decay time constants on the electron energy deposit is observed, the results are not statistically significant.

Convoy electron emission from resonant coherently excited 390 MeV/u hydrogen-like Ar ions

NASA Astrophysics Data System (ADS)

Azuma, T.; Takabayashi, Y.; Ito, T.; Komaki, K.; Yamazaki, Y.; Takada, E.; Murakami, T.

2003-12-01

Energetic ions traveling through a single crystal are excited by an oscillating crystal field produced by a periodic arrangement of the atomic strings/planes, which is called Resonant Coherent Excitation (RCE). We have observed enhancement of convoy electron yields associated with RCE of 1s electron to the n=2 excited states of 390 MeV/u hydrogen-like Ar 17+ ions passing through a Si crystal in the (2 2¯ 0) planar channeling condition. Lost electrons from projectile ions due to ionization contribute to convoy electrons emitted in the forward direction with the same velocity as the projectile ions. With combination of a magnet and a thick Si solid-state detector, we measured the energy spectra of convoy electrons of about 200 keV emitted at 0°. The convoy electron yield as a function of the transition energy, i.e. the resonance profile, has a similar structure to the resonance profile observed through the ionized fraction of the emerging ions. It is explained by the fact that both enhancements are due to increase in the fraction of the excited states from which electrons are more easily ionized by target electron impact in the crystal than from the ground state.

Fourier Transform Mass Spectrometry and Nuclear Magnetic Resonance Analysis for the Rapid and Accurate Characterization of Hexacosanoylceramide.

PubMed

Ross, Charles W; Simonsick, William J; Bogusky, Michael J; Celikay, Recep W; Guare, James P; Newton, Randall C

2016-06-28

Ceramides are a central unit of all sphingolipids which have been identified as sites of biological recognition on cellular membranes mediating cell growth and differentiation. Several glycosphingolipids have been isolated, displaying immunomodulatory and anti-tumor activities. These molecules have generated considerable interest as potential vaccine adjuvants in humans. Accurate analyses of these and related sphingosine analogues are important for the characterization of structure, biological function, and metabolism. We report the complementary use of direct laser desorption ionization (DLDI), sheath flow electrospray ionization (ESI) Fourier transform ion cyclotron resonance mass spectrometry (FTICR MS) and high-field nuclear magnetic resonance (NMR) analysis for the rapid, accurate identification of hexacosanoylceramide and starting materials. DLDI does not require stringent sample preparation and yields representative ions. Sheath-flow ESI yields ions of the product and byproducts and was significantly better than monospray ESI due to improved compound solubility. Negative ion sheath flow ESI provided data of starting materials and products all in one acquisition as hexacosanoic acid does not ionize efficiently when ceramides are present. NMR provided characterization of these lipid molecules complementing the results obtained from MS analyses. NMR data was able to differentiate straight chain versus branched chain alkyl groups not easily obtained from mass spectrometry.

Transient charge-masking effect of applied voltage on electrospinning of pure chitosan nanofibers from aqueous solutions.

PubMed

Terada, Dohiko; Kobayashi, Hisatoshi; Zhang, Kun; Tiwari, Ashutosh; Yoshikawa, Chiaki; Hanagata, Nobutaka

2012-02-01

The processing of a polyelectrolyte (whose functionality is derived from its ionized functional groups) into a nanofiber may improve its functionality and yield multiple functionalities. However, the electrospinning of nanofibers from polyelectrolytes is imperfect because polyelectrolytes differ considerably from neutral polymers in their rheological properties. In our study, we attempt to solve this problem by applying a voltage of opposite polarity to charges on a polyelectrolyte. The application of this 'countervoltage' can temporarily mask or screen a specific rheological property of the polyelectrolyte, making it behave as a neutral polymer. This approach can significantly contribute to the development of new functional nanofiber materials.

STRUCTURAL DETERMINATION AND QUANTITATIVE ANALYSIS OF BACTERIAL PHOSPHOLIPIDS USING LIQUID CHROMATOGRAPHY/ELECTROSPRAY IONIZATION/MASS SPECTROMETRY

EPA Science Inventory

This report presents a comprehensive spectral analysis of common bacterial phospholipids using electrospray/mass spectrometry (ESI/MS) under both negative and positive ionization conditions. Phospholipids under positive ionization yield sodium-adduct molecular ions which are mos...

Electron ionization of SiCl4

NASA Astrophysics Data System (ADS)

King, Simon J.; Price, Stephen D.

2011-02-01

Relative partial ionization cross sections (PICS) for the formation of fragment ions following electron ionization of SiCl4, in the electron energy range 30-200 eV, have been determined using time-of-flight mass spectrometry coupled with an ion coincidence technique. By this method, the contributions to the yield of each fragment ion from dissociative single, double, and triple ionization, are distinguished. These yields are quantified in the form of relative precursor-specific PICS, which are reported here for the first time for SiCl4. For the formation of singly charged ionic fragments, the low-energy maxima appearing in the PICS curves are due to contributions from single ionization involving predominantly indirect ionization processes, while contributions to the yields of these ions at higher electron energies are often dominated by dissociative double ionization. Our data, in the reduced form of relative PICS, are shown to be in good agreement with a previous determination of the PICS of SiCl4. Only for the formation of doubly charged fragment ions are the current relative PICS values lower than those measured in a previous study, although both datasets agree within combined error limits. The relative PICS data presented here include the first quantitative measurements of the formation of Cl2+ fragment ions and of the formation of ion pairs via dissociative double ionization. The peaks appearing in the 2D ion coincidence data are analyzed to provide further information concerning the mechanism and energetics of the charge-separating dissociations of SiCl42+. The lowest energy dicationic precursor state, leading to SiCl3+ + Cl+ formation, lies 27.4 ± 0.3 eV above the ground state of SiCl4 and is in close agreement with a calculated value of the adiabatic double ionization energy (27.3 eV).

Electron ionization of SiCl4.

PubMed

King, Simon J; Price, Stephen D

2011-02-21

Relative partial ionization cross sections (PICS) for the formation of fragment ions following electron ionization of SiCl(4), in the electron energy range 30-200 eV, have been determined using time-of-flight mass spectrometry coupled with an ion coincidence technique. By this method, the contributions to the yield of each fragment ion from dissociative single, double, and triple ionization, are distinguished. These yields are quantified in the form of relative precursor-specific PICS, which are reported here for the first time for SiCl(4). For the formation of singly charged ionic fragments, the low-energy maxima appearing in the PICS curves are due to contributions from single ionization involving predominantly indirect ionization processes, while contributions to the yields of these ions at higher electron energies are often dominated by dissociative double ionization. Our data, in the reduced form of relative PICS, are shown to be in good agreement with a previous determination of the PICS of SiCl(4). Only for the formation of doubly charged fragment ions are the current relative PICS values lower than those measured in a previous study, although both datasets agree within combined error limits. The relative PICS data presented here include the first quantitative measurements of the formation of Cl(2) (+) fragment ions and of the formation of ion pairs via dissociative double ionization. The peaks appearing in the 2D ion coincidence data are analyzed to provide further information concerning the mechanism and energetics of the charge-separating dissociations of SiCl(4) (2+). The lowest energy dicationic precursor state, leading to SiCl(3) (+) + Cl(+) formation, lies 27.4 ± 0.3 eV above the ground state of SiCl(4) and is in close agreement with a calculated value of the adiabatic double ionization energy (27.3 eV).

Electrospray Post-Ionization Mass Spectrometry of Electrosurgical Aerosols

NASA Astrophysics Data System (ADS)

Guenther, Sabine; Schäfer, Karl-Christian; Balog, Júlia; Dénes, Júlia; Majoros, Tamás; Albrecht, Katalin; Tóth, Miklós; Spengler, Bernhard; Takáts, Zoltán

2011-11-01

The feasibility of electrospray (ES) ionization of aerosols generated by electrosurgical disintegration methods was investigated. Although electrosurgery itself was demonstrated to produce gaseous ions, post-ionization methods were implemented to enhance the ion yield, especially in those cases when the ion current produced by the applied electrosurgical method is not sufficient for MS analysis. Post-ionization was implemented by mounting an ES emitter onto a Venturi pump, which is used for ion transfer. The effect of various parameters including geometry, high voltage setting, flow parameters, and solvent composition was investigated in detail. Experimental setups were optimized accordingly. ES post-ionization was found to yield spectra similar to those obtained by the REIMS technique, featuring predominantly lipid-type species. Signal enhancement was 20- to 50-fold compared with electrosurgical disintegration in positive mode, while no improvement was observed in negative mode. ES post-ionization was also demonstrated to allow the detection of non-lipid type species in the electrosurgical aerosol, including drug molecules. Since the tissue specificity of the MS data was preserved in the ES post-ionization setup, feasibility of tissue identification was demonstrated using different electrosurgical methods.

Color matters--material ejection and ion yields in UV-MALDI mass spectrometry as a function of laser wavelength and laser fluence.

PubMed

Soltwisch, Jens; Jaskolla, Thorsten W; Dreisewerd, Klaus

2013-10-01

The success of matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) as a widely employed analytical tool in the biomolecular sciences builds strongly on an effective laser-material interaction that is resulting in a soft co-desorption and ionization of matrix and imbedded biomolecules. To obtain a maximized ion yield for the analyte(s) of interest, in general both wavelength and fluence need to be tuned to match the specific optical absorption profile of the used matrix. However, commonly only lasers with fixed emission wavelengths of either 337 or 355 nm are used for MALDI-MS. Here, we employed a wavelength-tunable dye laser and recorded both the neutral material ejection and the MS ion data in a wide wavelength and fluence range between 280 and 377.5 nm. α-Cyano-4-hydroxycinnamic acid (HCCA), 4-chloro-α-cyanocinnamic acid (ClCCA), α-cyano-2,4-difluorocinnamic acid (DiFCCA), and 2,5-dihydroxybenzoic acid (DHB) were investigated as matrices, and several peptides as analytes. Recording of the material ejection was achieved by adopting a photoacoustic approach. Relative ion yields were derived by division of photoacoustic and ion signals. In this way, distinct wavelength/fluence regions can be identified for which maximum ion yields were obtained. For the tested matrices, optimal results were achieved for wavelengths corresponding to areas of high optical absorption of the respective matrix and at fluences about a factor of 2-3 above the matrix- and wavelength-dependent ion detection threshold fluences. The material ejection as probed by the photoacoustic method is excellently fitted by the quasithermal model, while a sigmoidal function allows for an empirical description of the ion signal-fluence relationship.

Total angular momenta of high-lying odd levels of U I at ∼ 4 eV using resonance ionization laser polarization spectroscopy

NASA Astrophysics Data System (ADS)

Rath, Asawari D.; Kundu, S.; Ray, A. K.

2018-02-01

Laser induced photoionization of atoms shows significant dependence on the choice of polarizations of lasers. In multi-step, multi-photon excitation and subsequent ionization of atoms different polarization combinations of the exciting lasers lead to distinctly different ion yields. This fact is exploited in this work to determine total angular momenta of odd-parity energy levels of U I lying at ∼ 4 eV from its ground level using resonance ionization laser polarization spectroscopy in time of flight mass spectrometer. These levels are populated by two-step resonant excitation using two pulsed dye lasers with preset polarizations of choice followed by nonresonant ionization by third laser. The dependence of ionization yield on specific polarizations of the first two lasers is studied experimentally for each level under consideration. This dependence when compared to simulations makes possible unambiguous assignment of J angular momenta to these levels.

Numerical quasi-linear study of the critical ionization velocity phenomenon

NASA Technical Reports Server (NTRS)

Moghaddam-Taaheri, E.; Goertz, C. K.

1993-01-01

The critical ionization velocity (CIV) for a neutral barium (Ba) gas cloud moving across the static magnetic field is studied numerically using quasi-linear equations and a parameter range which is typical for the shaped-charge Ba gas release experiments in space. For consistency the charge exchange between the background oxygen ions and neutral atoms and its reverse process, as well as the excitation of the neutral Ba atoms, are included. The numerical results indicate that when the ionization rate due to CIV becomes comparable to the charge exchange rate the energy lost to the ionization and excitation collisions by the superthermal electrons exceeds the energy gain from the waves that are excited by the ion beam. This results in a CIV yield less than the yield by the charge exchange process.

Analytical solutions for avalanche-breakdown voltages of single-diffused Gaussian junctions

NASA Astrophysics Data System (ADS)

Shenai, K.; Lin, H. C.

1983-03-01

Closed-form solutions of the potential difference between the two edges of the depletion layer of a single diffused Gaussian p-n junction are obtained by integrating Poisson's equation and equating the magnitudes of the positive and negative charges in the depletion layer. By using the closed form solution of the static Poisson's equation and Fulop's average ionization coefficient, the ionization integral in the depletion layer is computed, which yields the correct values of avalanche breakdown voltage, depletion layer thickness at breakdown, and the peak electric field as a function of junction depth. Newton's method is used for rapid convergence. A flowchart to perform the calculations with a programmable hand-held calculator, such as the TI-59, is shown.

Generalization of dielectric-dependent hybrid functionals to finite systems

DOE PAGES

Brawand, Nicholas P.; Voros, Marton; Govoni, Marco; ...

2016-10-04

The accurate prediction of electronic and optical properties of molecules and solids is a persistent challenge for methods based on density functional theory. We propose a generalization of dielectric-dependent hybrid functionals to finite systems where the definition of the mixing fraction of exact and semilocal exchange is physically motivated, nonempirical, and system dependent. The proposed functional yields ionization potentials, and fundamental and optical gaps of many, diverse molecular systems in excellent agreement with experiments, including organic and inorganic molecules and semiconducting nanocrystals. As a result, we further demonstrate that this hybrid functional gives the correct alignment between energy levels ofmore » the exemplary TTF-TCNQ donor-acceptor system.« less

Double ionization of nitrogen molecules in orthogonal two-color femtosecond laser fields

NASA Astrophysics Data System (ADS)

Song, Qiying; Li, Hui; Wang, Junping; Lu, Peifen; Gong, Xiaochun; Ji, Qinying; Lin, Kang; Zhang, Wenbin; Ma, Junyang; Li, Hanxiao; Zeng, Heping; He, Feng; Wu, Jian

2018-04-01

Double ionization of nitrogen molecules in orthogonally polarized two-color femtosecond laser fields is investigated by varying the relative intensity between the fundamental wave (FW) and its second harmonic (SH) components. The yield ratios of the double ionization channels, i.e., the non-dissociative {{{{N}}}2}2+ and Coulomb exploded (N+, N+), to the singly charged N2 + channel exhibit distinct dependences on the relative strength between the FW and SH fields. As the intensity ratio of SH to FW increases, the yield ratio of (N+, N+)/N2 + gradually increases, while the ratio of {{{{N}}}2}2+/N2 + first descends and then increases constituting a valley shape which is similar to the behavior of Ar2+/Ar+ observed in the same experimental condition. Based on the classical trajectory simulations, we found that the different characteristics of the two doubly ionized channels stem from two mechanisms, i.e., the {{{{N}}}2}2+ is mostly accessed by the (e, 2e) impact ionization while the recollision-induced excitation with subsequent ionization plays an important role in producing the (N+, N+) channel.

Attosecond Spectroscopy Probing Electron Correlation Dynamics

NASA Astrophysics Data System (ADS)

Winney, Alexander H.

Electrons are the driving force behind every chemical reaction. The exchange, ionization, or even relaxation of electrons is behind every bond broken or formed. According to the Bohr model of the atom, it takes an electron 150 as to orbit a proton[6]. With this as a unit time scale for an electron, it is clear that a pulse duration of several femtoseconds will not be sufficient to understanding electron dynamics. Our work demonstrates both technical and scientific achievements that push the boundaries of attosecond dynamics. TDSE studies show that amplification the yield of high harmonic generation (HHG) may be possible with transverse confinement of the electron. XUV-pump-XUV-probe shows that the yield of APT train can be sufficient for 2-photon double ionization studies. A zero dead-time detection system allows for the measurement of state-resolved double ionization for the first time. Exploiting attosecond angular streaking[7] probes sequential and non-sequential double ionization via electron-electron correlations with attosecond time resolution. Finally, using recoil frame momentum correlation, the fast dissociation of CH 3I reveals important orbital ionization dynamics of non-dissociative & dissociative, single & double ionization.

Comparison study for multiple ionization of carbonyl sulfide by linearly and circularly polarized intense femtosecond laser fields using Coulomb explosion imaging

NASA Astrophysics Data System (ADS)

Ma, Pan; Wang, Chuncheng; Luo, Sizuo; Yu, Xitao; Li, Xiaokai; Wang, Zhenzhen; Hu, Wenhui; Yu, Jiaqi; Yang, Yizhang; Tian, Xu; Cui, Zhonghua; Ding, Dajun

2018-05-01

We studied the relative yields and dissociation dynamics for two- and three-body Coulomb explosion (CE) channels from highly charged carbonyl sulfide molecules in intense laser fields using the CE imaging technique. The electron recollision contributions are evaluated by comparing the relative yields for the multiple ionization process in linearly polarized and circularly polarized (LP and CP) laser fields. The nonsequential multiple ionization is only confirmed for the charge states of 2 to 4 because the energy for further ionization from the inner orbital is much larger than the maximum recollision energy, 3.2U p . The novel deviations of kinetic energy releases distributions between LP and CP pulses are observed for the charge states higher than 4. It can be attributed to the stronger molecular bending in highly charged states before three-body CE with CP light, in which the bending wave packet is initialed by the triple or quartic ionization and spread along their potential curves. Compared to LP light, CP light ionizes a larger fraction of bending molecules in the polarization plane.

Degradation spectra and ionization yields of electrons in gases

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

Inokuti, M.; Douthat, D.A.; Rau, A.R.P.

1975-01-01

Progress in the microscopic theory of electron degradation in gases by Platzman, Fano, and co-workers is outlined. The theory consists of (1) the cataloging of all major inelastic-collision cross sections for electrons (including secondary-electron energy distribution in a single ionizing collision) and (2) the evaluation of cumulative consequences of individual electron collisions for the electrons themselves as well as for target molecules. For assessing the data consistency and reliability and extrapolating the data to the unexplored ranges of variables (such as electron energy), a series of plots devised by Platzman are very powerful. Electron degradation spectra were obtained through numericalmore » solution of the Spencer--Fano equation for all electron energies down to the first ionization thresholds for a few examples such as He and Ne. The systematics of the solutions resulted in the recognition of approximate scaling properties of the degradation spectra for different initial electron energies and pointed to new methods of more efficient treatment. Systematics of the ionization yields and their energy dependence on the initial electron energy were also recognized. Finally, the Spencer--Fano equation for the degradation spectra and the Fowler equation for the ionization and other yields are tightly linked with each other by a set of variational principles. (52 references, 7 figures) (DLC)« less

Deep UV emitting scintillators for alpha and beta particle detection

NASA Astrophysics Data System (ADS)

Zhou, Y.; Jia, D. D.; Lewis, L. A.; Feofilov, S. P.; Meltzer, R. S.

2011-03-01

Several deep UV emitting scintillators, whose emission falls in the solar blind region of the spectrum (200-280 nm), are described and their scintillator properties are characterized. They include LaPO 4:Pr, YPO 4:Pr, YAlO 3:Pr, Pr(PO 3) 3, YPO 4:Bi and ScPO 4. These materials would facilitate the detection of ionizing radiation in open areas, even during the daylight hours, and could be used to support large area surveys that monitor for the presence of ionization radiation due, for example, to system leaks or transfer contamination. These materials can be used in the form of powders, thin films or paints for radiation detection. They are characterized for both beta radiation using electron beams (2-35 keV) and 137Cs and alpha radiations using 241Am sources. Their absolute light yields are estimated and are compared to that of Y 2SiO 5:Ce. Their light yields decrease as a function of electron energy but at 10 keV they approach 8000 ph/MeV.

Synchrotron-based valence shell photoionization of CH radical

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

Gans, B., E-mail: berenger.gans@u-psud.fr, E-mail: christian.alcaraz@u-psud.fr; Falvo, C.; Holzmeier, F.

2016-05-28

We report the first experimental observations of X{sup +} {sup 1}Σ{sup +}←X {sup 2}Π and a{sup +} {sup 3}Π←X {sup 2}Π single-photon ionization transitions of the CH radical performed on the DESIRS beamline at the SOLEIL synchrotron facility. The radical was produced by successive hydrogen-atom abstractions on methane by fluorine atoms in a continuous microwave discharge flow tube. Mass-selected ion yields and photoelectron spectra were recorded as a function of photon energy using a double imaging photoelectron/photoion coincidence spectrometer. The ion yield appears to be strongly affected by vibrational and electronic autoionizations, which allow the observation of high Rydberg statesmore » of the neutral species. The photoelectron spectra enable the first direct determinations of the adiabatic ionization potential and the energy of the first triplet state of the cation with respect to its singlet ground state. This work also brings valuable information on the complex electronic structure of the CH radical and its cation and adds new observations to complement our understanding of Rydberg states and autoionization processes.« less

Ion energies in high power impulse magnetron sputtering with and without localized ionization zones

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

Yang, Yuchen; Lawrence Berkeley National Laboratory, 1 Cyclotron Road, Berkeley, California 94720; Tanaka, Koichi

2015-03-23

High speed imaging of high power impulse magnetron sputtering discharges has revealed that ionization is localized in moving ionization zones but localization disappears at high currents for high yield targets. This offers an opportunity to study the effect ionization zones have on ion energies. We measure that ions have generally higher energies when ionization zones are present, supporting the concept that these zones are associated with moving potential humps. We propose that the disappearance of ionization zones is caused by an increased supply of atoms from the target which cools electrons and reduces depletion of atoms to be ionized.

Computational tests of quantum chemical models for excited and ionized states of molecules with phosphorus and sulfur atoms.

PubMed

Hahn, David K; RaghuVeer, Krishans; Ortiz, J V

2014-05-15

Time-dependent density functional theory (TD-DFT) and electron propagator theory (EPT) are used to calculate the electronic transition energies and ionization energies, respectively, of species containing phosphorus or sulfur. The accuracy of TD-DFT and EPT, in conjunction with various basis sets, is assessed with data from gas-phase spectroscopy. TD-DFT is tested using 11 prominent exchange-correlation functionals on a set of 37 vertical and 19 adiabatic transitions. For vertical transitions, TD-CAM-B3LYP calculations performed with the MG3S basis set are lowest in overall error, having a mean absolute deviation from experiment of 0.22 eV, or 0.23 eV over valence transitions and 0.21 eV over Rydberg transitions. Using a larger basis set, aug-pc3, improves accuracy over the valence transitions via hybrid functionals, but improved accuracy over the Rydberg transitions is only obtained via the BMK functional. For adiabatic transitions, all hybrid functionals paired with the MG3S basis set perform well, and B98 is best, with a mean absolute deviation from experiment of 0.09 eV. The testing of EPT used the Outer Valence Green's Function (OVGF) approximation and the Partial Third Order (P3) approximation on 37 vertical first ionization energies. It is found that OVGF outperforms P3 when basis sets of at least triple-ζ quality in the polarization functions are used. The largest basis set used in this study, aug-pc3, obtained the best mean absolute error from both methods -0.08 eV for OVGF and 0.18 eV for P3. The OVGF/6-31+G(2df,p) level of theory is particularly cost-effective, yielding a mean absolute error of 0.11 eV.

Electron impact ionization of the gas-phase sorbitol

NASA Astrophysics Data System (ADS)

Chernyshova, Irina; Markush, Pavlo; Zavilopulo, Anatoly; Shpenik, Otto

2015-03-01

Ionization and dissociative ionization of the sorbitol molecule by electron impact have been studied using two different experimental methods. In the mass range of m/ z = 10-190, the mass spectra of sorbitol were recorded at the ionizing electron energies of 70 and 30 eV. The ion yield curves for the fragment ions have been analyzed and the appearance energies of these ions have been determined. The relative total ionization cross section of the sorbitol molecule was measured using monoenergetic electron beam. Possible fragmentation pathways for the sorbitol molecule were proposed.

A Physical Model for the Evolving Ultraviolet Luminosity Function of High Redshift Galaxies and their Contribution to the Cosmic Reionization

NASA Astrophysics Data System (ADS)

Cai, Zhen-Yi; Lapi, Andrea; Bressan, Alessandro; De Zotti, Gianfranco; Negrello, Mattia; Danese, Luigi

2014-04-01

We present a physical model for the evolution of the ultraviolet (UV) luminosity function of high-redshift galaxies, taking into account in a self-consistent way their chemical evolution and the associated evolution of dust extinction. Dust extinction is found to increase fast with halo mass. A strong correlation between dust attenuation and halo/stellar mass for UV selected high-z galaxies is thus predicted. The model yields good fits of the UV and Lyman-α (Lyα) line luminosity functions at all redshifts at which they have been measured. The weak observed evolution of both luminosity functions between z = 2 and z = 6 is explained as the combined effect of the negative evolution of the halo mass function; of the increase with redshift of the star formation efficiency due to the faster gas cooling; and of dust extinction, differential with halo mass. The slope of the faint end of the UV luminosity function is found to steepen with increasing redshift, implying that low luminosity galaxies increasingly dominate the contribution to the UV background at higher and higher redshifts. The observed range of the UV luminosities at high z implies a minimum halo mass capable of hosting active star formation M crit <~ 109.8 M ⊙, which is consistent with the constraints from hydrodynamical simulations. From fits of Lyα line luminosity functions, plus data on the luminosity dependence of extinction, and from the measured ratios of non-ionizing UV to Lyman-continuum flux density for samples of z ~= 3 Lyman break galaxies and Lyα emitters, we derive a simple relationship between the escape fraction of ionizing photons and the star formation rate. It implies that the escape fraction is larger for low-mass galaxies, which are almost dust-free and have lower gas column densities. Galaxies already represented in the UV luminosity function (M UV <~ -18) can keep the universe fully ionized up to z ~= 6. This is consistent with (uncertain) data pointing to a rapid drop of the ionization degree above z ~= 6, such as indications of a decrease of the comoving emission rate of ionizing photons at z ~= 6, a decrease of sizes of quasar near zones, and a possible decline of the Lyα transmission through the intergalactic medium at z > 6. On the other hand, the electron scattering optical depth, τes, inferred from cosmic microwave background (CMB) experiments favor an ionization degree close to unity up to z ~= 9-10. Consistency with CMB data can be achieved if M crit ~= 108.5 M ⊙, implying that the UV luminosity functions extend to M UV ~= -13, although the corresponding τes is still on the low side of CMB-based estimates.

Constraining the contribution of active galactic nuclei to reionization

NASA Astrophysics Data System (ADS)

Hassan, Sultan; Davé, Romeel; Mitra, Sourav; Finlator, Kristian; Ciardi, Benedetta; Santos, Mario G.

2018-01-01

Recent results have suggested that active galactic nuclei (AGN) could provide enough photons to reionize the Universe. We assess the viability of this scenario using a semi-numerical framework for modelling reionization, to which we add a quasar contribution by constructing a Quasar Halo Occupancy Distribution (QHOD) based on Giallongo et al. observations. Assuming a constant QHOD, we find that an AGN-only model cannot simultaneously match observations of the optical depth τe, neutral fraction and ionizing emissivity. Such a model predicts τe too low by ∼2σ relative to Planck constraints, and reionizes the Universe at z ≲ 5. Arbitrarily increasing the AGN emissivity to match these results yields a strong mismatch with the observed ionizing emissivity at z ∼ 5. If we instead assume a redshift-independent AGN luminosity function yielding an emissivity evolution like that assumed in Madau & Haardt model, then we can match τe albeit with late reionization; however, such evolution is inconsistent with observations at z ∼ 4-6 and poorly motivated physically. These results arise because AGN are more biased towards massive haloes than typical reionizing galaxies, resulting in stronger clustering and later formation times. AGN-dominated models produce larger ionizing bubbles that are reflected in ∼×2 more 21 cm power on all scales. A model with equal part galaxies and AGN contribution is still (barely) consistent with observations, but could be distinguished using next-generation 21 cm experiments such as Hydrogen Epoch of Reionization Array and SKA-low. We conclude that, even with recent claims of more faint AGN than previously thought, AGN are highly unlikely to dominate the ionizing photon budget for reionization.

Accurate Valence Ionization Energies from Kohn-Sham Eigenvalues with the Help of Potential Adjustors.

PubMed

Thierbach, Adrian; Neiss, Christian; Gallandi, Lukas; Marom, Noa; Körzdörfer, Thomas; Görling, Andreas

2017-10-10

An accurate yet computationally very efficient and formally well justified approach to calculate molecular ionization potentials is presented and tested. The first as well as higher ionization potentials are obtained as the negatives of the Kohn-Sham eigenvalues of the neutral molecule after adjusting the eigenvalues by a recently [ Görling Phys. Rev. B 2015 , 91 , 245120 ] introduced potential adjustor for exchange-correlation potentials. Technically the method is very simple. Besides a Kohn-Sham calculation of the neutral molecule, only a second Kohn-Sham calculation of the cation is required. The eigenvalue spectrum of the neutral molecule is shifted such that the negative of the eigenvalue of the highest occupied molecular orbital equals the energy difference of the total electronic energies of the cation minus the neutral molecule. For the first ionization potential this simply amounts to a ΔSCF calculation. Then, the higher ionization potentials are obtained as the negatives of the correspondingly shifted Kohn-Sham eigenvalues. Importantly, this shift of the Kohn-Sham eigenvalue spectrum is not just ad hoc. In fact, it is formally necessary for the physically correct energetic adjustment of the eigenvalue spectrum as it results from ensemble density-functional theory. An analogous approach for electron affinities is equally well obtained and justified. To illustrate the practical benefits of the approach, we calculate the valence ionization energies of test sets of small- and medium-sized molecules and photoelectron spectra of medium-sized electron acceptor molecules using a typical semilocal (PBE) and two typical global hybrid functionals (B3LYP and PBE0). The potential adjusted B3LYP and PBE0 eigenvalues yield valence ionization potentials that are in very good agreement with experimental values, reaching an accuracy that is as good as the best G 0 W 0 methods, however, at much lower computational costs. The potential adjusted PBE eigenvalues result in somewhat less accurate ionization energies, which, however, are almost as accurate as those obtained from the most commonly used G 0 W 0 variants.

Ionization, evaporation and fragmentation of C60 in collisions with highly charged C, O and F ions—effect of projectile charge state.

NASA Astrophysics Data System (ADS)

Kelkar, A. H.; Misra, D.; Tribedi, L. C.

2007-09-01

We study the various inelastic processes such ionization, fragmentation and evaporation of C60 molecule in collisions with fast heavy ions. We have used 2.33 MeV/u C, O and F projectile ion beams. Various ionization and fragmentation products were detected using time-of-flight mass spectrometer. The multiply charged C60r+ ions were detected for maximum r = 4. The projectile charge state (qp) dependence of the single and double ionization cross sections is well reproduced by a model based on the giant dipole plasmon resonance (GDPR). The qp-dependence of the fragmentation yields, was found to be linear. Variation of relative yields of the evaporation products of C602+ (i.e. C582+, C562+ etc) and C603+ (i.e. C583+, C563+ etc) with qp has also been investigated for various projectiles.

Dissociative-ionization cross sections for 12-keV-electron impact on CO{sub 2}

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

Bhatt, Pragya; Singh, Raj; Yadav, Namita

The dissociative ionization of a CO{sub 2} molecule is studied at an electron energy of 12 keV using the multiple ion coincidence imaging technique. The absolute partial ionization cross sections and the precursor-specific absolute partial ionization cross sections of resulting fragment ions are obtained and reported. It is found that {approx}75% of single ionization, 22% of double ionization, and {approx}2% of triple ionization of the parent molecule contribute to the total fragment ion yield; quadruple ionization of CO{sub 2} is found to make a negligibly small contribution. Furthermore, the absolute partial ionization cross sections for ion-pair and ion-triple formation aremore » measured for nine dissociative ionization channels of up to a quadruply ionized CO{sub 2} molecule. In addition, the branching ratios for single-ion, ion-pair, and ion-triple formation are also determined.« less

Determination of relative ion chamber calibration coefficients from depth-ionization measurements in clinical electron beams

NASA Astrophysics Data System (ADS)

Muir, B. R.; McEwen, M. R.; Rogers, D. W. O.

2014-10-01

A method is presented to obtain ion chamber calibration coefficients relative to secondary standard reference chambers in electron beams using depth-ionization measurements. Results are obtained as a function of depth and average electron energy at depth in 4, 8, 12 and 18 MeV electron beams from the NRC Elekta Precise linac. The PTW Roos, Scanditronix NACP-02, PTW Advanced Markus and NE 2571 ion chambers are investigated. The challenges and limitations of the method are discussed. The proposed method produces useful data at shallow depths. At depths past the reference depth, small shifts in positioning or drifts in the incident beam energy affect the results, thereby providing a built-in test of incident electron energy drifts and/or chamber set-up. Polarity corrections for ion chambers as a function of average electron energy at depth agree with literature data. The proposed method produces results consistent with those obtained using the conventional calibration procedure while gaining much more information about the behavior of the ion chamber with similar data acquisition time. Measurement uncertainties in calibration coefficients obtained with this method are estimated to be less than 0.5%. These results open up the possibility of using depth-ionization measurements to yield chamber ratios which may be suitable for primary standards-level dissemination.

Ion Yields in the Coupled Chemical and Physical Dynamics Model of Matrix-Assisted Laser Desorption/Ionization

NASA Astrophysics Data System (ADS)

Knochenmuss, Richard

2015-08-01

The Coupled Chemical and Physical Dynamics (CPCD) model of matrix assisted laser desorption ionization has been restricted to relative rather than absolute yield comparisons because the rate constant for one step in the model was not accurately known. Recent measurements are used to constrain this constant, leading to good agreement with experimental yield versus fluence data for 2,5-dihydroxybenzoic acid. Parameters for alpha-cyano-4-hydroxycinnamic acid are also estimated, including contributions from a possible triplet state. The results are compared with the polar fluid model, the CPCD is found to give better agreement with the data.

Orbital Picture of Ionization and Its Breakdown in Nanoarrays of Quantum Dots

NASA Astrophysics Data System (ADS)

Bâldea, Ioan; Cederbaum, Lorenz S.

2002-09-01

We present exact numerical results indicating that ionization could be a useful tool to study electron correlations in artificial molecules and nanoarrays of metallic quantum dots. For nanorings consisting of Ag quantum dots of the type already fabricated, we demonstrate that the molecular orbital picture breaks down even for lowest energy ionization processes, in contrast to ordinary molecules. Our ionization results yield a transition point between localization and delocalization regimes in good agreement with various experimental data.

UV Lamp as a Facile Ozone Source for Structural Analysis of Unsaturated Lipids Via Electrospray Ionization-Mass Spectrometry

NASA Astrophysics Data System (ADS)

Stinson, Craig A.; Zhang, Wenpeng; Xia, Yu

2017-12-01

Ozonolysis of alkene functional groups is a type of highly specific and effective chemical reaction, which has found increasing applications in structural analysis of unsaturated lipids via coupling with mass spectrometry (MS). In this work, we utilized a low-pressure mercury lamp (6 W) to initiate ozonolysis inside electrospray ionization (ESI) sources. By placing the lamp near a nanoESI emitter that partially transmits 185 nm ultraviolet (UV) emission from the lamp, dissolved dioxygen in the spray solution was converted into ozone, which subsequently cleaved the double bonds within fatty acyls of lipids. Solvent conditions, such as presence of water and acid solution pH, were found to be critical in optimizing ozonolysis yields. Fast (on seconds time scale) and efficient (50%-100% yield) ozonolysis was achieved for model unsaturated phospholipids and fatty acids with UV lamp-induced ozonolysis incorporated on a static and an infusion nanoESI source. The method was able to differentiate double bond location isomers and identify the geometry of the double bond based on yield. The analytical utility of UV lamp-induced ozonolysis was further demonstrated by implementation on a liquid chromatography (LC)-MS platform. Ozonolysis was effected in a flow microreactor that was made from ozone permeable tubing, so that ambient ozone produced by the lamp irradiation could diffuse into the reactor and induce online ozonolysis post-LC separation and before ESI-MS.

Proton beam dosimetry: a comparison between a plastic scintillator, ionization chamber and Faraday cup.

PubMed

Ghergherehchi, Mitra; Afarideh, Hossein; Ghannadi, Mohammad; Mohammadzadeh, Ahmad; Aslani, Golam Reza; Boghrati, Behzad

2010-01-01

In this study, a comparison was made between a plastic scintillator (BC400), a Faraday Cup (FC) and an ionization chamber (IC) used for routine proton dosimetry. Thin scintillators can be applied to proton dosimetry and consequently to proton therapy as relative dosimeters because of their water-equivalent nature, high energy-light conversion efficiency, low dimensions and good proportionality to the absorbed dose at low stopping powers. To employ such scintillators as relative dosimeters in proton therapy, the corrective factors must be applied to correct the quenching luminescence at the Bragg peak. A fine linear proportionality between the luminescence light yield Y and the proton flux in a thin (0.5 mm) scintillator for the 20 and 30 MeV proton beams were observed. The experimental peak/plateau ratios of Bragg Curve for 2, 1 and 0.5 mm scintillators with an accuracy of 0.5% were obtained to be 1.87, 1.91 and 2.30, respectively. With combination of the Markus chamber and the CR-39 detector, the peak/plateau ratio was improved to 3.26. The obtained data of the luminescence yield as a function of the specific energy loss is in agreement with the Craun-Birk's theory. Results show that the FC and Markus ionization chamber are in agreement within 4%, while the FC gives a lower dose evaluation. For a defined beam, the data for the fluence measurements are reproducible within a good accuracy.

Multiple ionization of neon by soft x-rays at ultrahigh intensity

NASA Astrophysics Data System (ADS)

Guichard, R.; Richter, M.; Rost, J.-M.; Saalmann, U.; Sorokin, A. A.; Tiedtke, K.

2013-08-01

At the free-electron laser FLASH, multiple ionization of neon atoms was quantitatively investigated at photon energies of 93.0 and 90.5 eV. For ion charge states up to 6+, we compare the respective absolute photoionization yields with results from a minimal model and an elaborate description including standard sequential and direct photoionization channels. Both approaches are based on rate equations and take into account a Gaussian spatial intensity distribution of the laser beam. From the comparison we conclude that photoionization up to a charge of 5+ can be described by the minimal model which we interpret as sequential photoionization assisted by electron shake-up processes. For higher charges, the experimental ionization yields systematically exceed the elaborate rate-based prediction.

Mechanisms of strand break formation in DNA due to the direct effect of ionizing radiation: the dependency of free base release on the length of alternating CG oligodeoxynucleotides.

PubMed

Sharma, Kiran K; Razskazovskiy, Yuriy; Purkayastha, Shubhadeep; Bernhard, William A

2009-06-11

The question of how NA base sequence influences the yield of DNA strand breaks produced by the direct effect of ionizing radiation was investigated in a series of oligodeoxynucleotides of the form (d(CG)(n))(2) and (d(GC)(n))(2). The yields of free base release from X-irradiated DNA films containing 2.5 waters/nucleotide were measured by HPLC as a function of oligomer length. For (d(CG)(n))(2), the ratio of the Gua yield to Cyt yield, R, was relatively constant at 2.4-2.5 for n = 2-4 and it decreased to 1.2 as n increased from 5 to 10. When Gua was moved to the 5' end, for example going from d(CG)(5) to d(GC)(5), R dropped from 1.9 +/- 0.1 to 1.1 +/- 0.1. These effects are poorly described if the chemistry at the oligomer ends is assumed to be independent of the remainder of the oligomer. A mathematical model incorporating charge transfer through the base stack was derived to explain these effects. In addition, EPR was used to measure the yield of trapped-deoxyribose radicals at 4 K following X-irradiation at 4 K. The yield of free base release was substantially greater, by 50-100 nmol/J, than the yield of trapped-deoxyribose radicals. Therefore, a large fraction of free base release stems from a nonradical intermediate. For this intermediate, a deoxyribose carbocation formed by two one-electron oxidations is proposed. This reaction pathway requires that the hole (electron loss site) transfers through the base stack and, upon encountering a deoxyribose hole, oxidizes that site to form a deoxyribose carbocation. This reaction mechanism provides a consistent way of explaining both the absence of trapped radical intermediates and the unusual dependence of free base release on oligomer length.

Molecular and supramolecular control of the work function of an inorganic electrode with self-assembled monolayer of umbrella-shaped fullerene derivatives.

PubMed

Lacher, Sebastian; Matsuo, Yutaka; Nakamura, Eiichi

2011-10-26

The surface properties of inorganic substrates can be altered by coating with organic molecules, which may result in the improvement of the properties suitable for electronic or biological applications. This article reports a systematic experimental study on the influence of the molecular and supramolecular properties of umbrella-shaped penta(organo)[60]fullerene derivatives, and on the work function and the water contact angle of indium-tin oxide (ITO) and gold surfaces. We could relate these macroscopic characteristics to single-molecular level properties, such as ionization potential and molecular dipole. The results led us to conclude that the formation of a SAM of a polar compound generates an electronic field through intermolecular interaction of the molecular charges, and this field makes the overall dipole of the SAM much smaller than the one expected from the simple sum of the dipoles of all molecules in the SAM. This effect, which was called depolarization and previously discussed theoretically, is now quantitatively probed by experiments. The important physical properties in surface science such as work function, ionization potential, and water contact angles have been mutually correlated at the level of molecular structures and molecular orientations on the substrate surface. We also found that the SAMs on ITO and gold operate under the same principle except that the "push-back" effect operates specifically for gold. The study also illustrates the ability of the photoelectron yield spectroscopy technique to rapidly measure the work function of a SAM-covered substrate and the ionization potential value of a molecule on the surface.

Resonantly Enhanced Betatron Hard X-rays from Ionization Injected Electrons in a Laser Plasma Accelerator

PubMed Central

Huang, K.; Li, Y. F.; Li, D. Z.; Chen, L. M.; Tao, M. Z.; Ma, Y.; Zhao, J. R.; Li, M. H.; Chen, M.; Mirzaie, M.; Hafz, N.; Sokollik, T.; Sheng, Z. M.; Zhang, J.

2016-01-01

Ultrafast betatron x-ray emission from electron oscillations in laser wakefield acceleration (LWFA) has been widely investigated as a promising source. Betatron x-rays are usually produced via self-injected electron beams, which are not controllable and are not optimized for x-ray yields. Here, we present a new method for bright hard x-ray emission via ionization injection from the K-shell electrons of nitrogen into the accelerating bucket. A total photon yield of 8 × 108/shot and 108 photons with energy greater than 110 keV is obtained. The yield is 10 times higher than that achieved with self-injection mode in helium under similar laser parameters. The simulation suggests that ionization-injected electrons are quickly accelerated to the driving laser region and are subsequently driven into betatron resonance. The present scheme enables the single-stage betatron radiation from LWFA to be extended to bright γ-ray radiation, which is beyond the capability of 3rd generation synchrotrons. PMID:27273170

Effect of metal surfaces on matrix-assisted laser desorption/ionization analyte peak intensities.

PubMed

Kancharla, Vidhyullatha; Bashir, Sajid; Liu, Jingbo L; Ramirez, Oscar M; Derrick, Peter J; Beran, Kyle A

2017-10-01

Different metal surfaces in the form of transmission electron microscope grids were examined as support surfaces in matrix-assisted laser desorption/ionization time-of-flight mass spectrometry with a view towards enhancement of peptide signal intensity. The observed enhancement between 5-fold and 20-fold relative to the normal stainless steel slide was investigated by applying the thermal desorption model for matrix-assisted laser desorption/ionization. A simple model evaluates the impact that the thermal properties of the metals have on the ion yield of the analyte. It was observed that there was not a direct, or strong, correlation between the thermal properties of the metals and the corresponding ion yield of the peptides. The effects of both fixed and variable laser irradiances versus ion yield were also examined for the respective metals studied. In all cases the use of transmission electron microscope grids required much lower laser irradiances in order to generate similar peak intensities as those observed with a stainless steel surface.

VUV photo-processing of PAH cations: quantitative study on the ionization versus fragmentation processes

PubMed Central

Zhen, Junfeng; Castillo, Sarah Rodriguez; Joblin, Christine; Mulas, Giacomo; Sabbah, Hassan; Giuliani, Alexandre; Nahon, Laurent; Martin, Serge; Champeaux, Jean-Philippe; Mayer, Paul M.

2016-01-01

Interstellar polycyclic aromatic hydrocarbons (PAHs) are strongly affected by the absorption of vacuum ultraviolet (VUV) photons in the interstellar medium (ISM), yet the branching ratio between ionization and fragmentation is poorly studied. This is crucial for the stability and charge state of PAHs in the ISM in different environments, affecting in turn the chemistry, the energy balance, and the contribution of PAHs to the extinction and emission curves. We studied the interaction of PAH cations with VUV photons in the 7 – 20 eV range from the synchrotron SOLEIL beamline, DESIRS. We recorded by action spectroscopy the relative intensities of photo-fragmentation and photo-ionization for a set of eight PAH cations ranging in size from 14 to 24 carbon atoms, with different structures. At photon energies below ~13.6 eV fragmentation dominates for the smaller species, while for larger species ionization is immediately competitive after the second ionization potential (IP). At higher photon energies, all species behave similarly, the ionization yield gradually increases, leveling off between 0.8 and 0.9 at ~18 eV. Among isomers, PAH structure appears to mainly affect the fragmentation cross section, but not the ionization cross section. We also measured the second IP for all species and the third IP for two of them, all are in good agreement with theoretical ones confirming that PAH cations can be further ionized in the diffuse ISM. Determining actual PAH dication abundances in the ISM will require detailed modeling. Our measured photo-ionization yields for several PAH cations provide a necessary ingredient for such models. PMID:27212712

VUV photo-processing of PAH cations: quantitative study on the ionization versus fragmentation processes.

PubMed

Zhen, Junfeng; Castillo, Sarah Rodriguez; Joblin, Christine; Mulas, Giacomo; Sabbah, Hassan; Giuliani, Alexandre; Nahon, Laurent; Martin, Serge; Champeaux, Jean-Philippe; Mayer, Paul M

2016-05-10

Interstellar polycyclic aromatic hydrocarbons (PAHs) are strongly affected by the absorption of vacuum ultraviolet (VUV) photons in the interstellar medium (ISM), yet the branching ratio between ionization and fragmentation is poorly studied. This is crucial for the stability and charge state of PAHs in the ISM in different environments, affecting in turn the chemistry, the energy balance, and the contribution of PAHs to the extinction and emission curves. We studied the interaction of PAH cations with VUV photons in the 7 - 20 eV range from the synchrotron SOLEIL beamline, DESIRS. We recorded by action spectroscopy the relative intensities of photo-fragmentation and photo-ionization for a set of eight PAH cations ranging in size from 14 to 24 carbon atoms, with different structures. At photon energies below ~13.6 eV fragmentation dominates for the smaller species, while for larger species ionization is immediately competitive after the second ionization potential (IP). At higher photon energies, all species behave similarly, the ionization yield gradually increases, leveling off between 0.8 and 0.9 at ~18 eV. Among isomers, PAH structure appears to mainly affect the fragmentation cross section, but not the ionization cross section. We also measured the second IP for all species and the third IP for two of them, all are in good agreement with theoretical ones confirming that PAH cations can be further ionized in the diffuse ISM. Determining actual PAH dication abundances in the ISM will require detailed modeling. Our measured photo-ionization yields for several PAH cations provide a necessary ingredient for such models.

Effect of multiple plasmon excitation on single, double and multiple ionizations of C60 in collisions with fast highly charged Si ions

NASA Astrophysics Data System (ADS)

Kelkar, A. H.; Kadhane, U.; Misra, D.; Kumar, A.; Tribedi, L. C.

2007-06-01

We have investigated the single and multiple ionizations of the C60 molecule in collisions with fast Siq+ projectiles for various projectile charge states (q) between q = 6 and 14. The q-dependence of the ionization cross sections and their ratios is compared with the giant dipole plasmon resonance (GDPR) model. The excellent qualitative agreement with the model in case of single and double ionizations and also a reasonable agreement with the triple (and to some extent with quadruple) ionization (without evaporation) yields signify dominant contributions of the single-, double- and triple-plasmon excitations on the single- and multiple-ionization process.

Triage of oxidation-prone proteins by Sqstm1/p62 within the mitochondria

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

Lee, Minjung; Shin, Jaekyoon, E-mail: jkshin@med.skku.ac.kr

2011-09-16

Highlights: {yields} The mitochondrion contains its own protein quality control system. {yields} p62 localizes within the mitochondria and forms mega-dalton sized complexes. {yields} p62 interacts with oxidation-prone proteins and the proteins of quality control. {yields} In vitro delivery of p62 improves mitochondrial functions. {yields} p62 is implicated as a participant in mitochondrial protein quality control. -- Abstract: As the mitochondrion is vulnerable to oxidative stress, cells have evolved several strategies to maintain mitochondrial integrity, including mitochondrial protein quality control mechanisms and autophagic removal of damaged mitochondria. Involvement of an autophagy adaptor, Sqstm1/p62, in the latter process has been recently described.more » In the present study, we provide evidence that a portion of p62 directly localizes within the mitochondria and supports stable electron transport by forming heterogeneous protein complexes. Matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF) of mitochondrial proteins co-purified with p62 revealed that p62 interacts with several oxidation-prone proteins, including a few components of the electron transport chain complexes, as well as multiple chaperone molecules and redox regulatory enzymes. Accordingly, p62-deficient mitochondria exhibited compromised electron transport, and the compromised function was partially restored by in vitro delivery of p62. These results suggest that p62 plays an additional role in maintaining mitochondrial integrity at the vicinity of target machineries through its function in relation to protein quality control.« less

Confined ion energy >200 keV and increased fusion yield in a DPF with monolithic tungsten electrodes and pre-ionization

NASA Astrophysics Data System (ADS)

Lerner, Eric J.; Hassan, Syed M.; Karamitsos, Ivana; Von Roessel, Fred

2017-10-01

To reduce impurities in the dense plasma focus FF-1 device, we used monolithic tungsten electrodes with pre-ionization. With this new set-up, we demonstrated a three-fold reduction of impurities by mass and a ten-fold reduction by ion number. FF-1 produced a 50% increase in fusion yield over our previous copper electrodes, both for a single shot and for a mean of ten consecutive shots with the same conditions. These results represent a doubling of fusion yield as compared with any other plasma focus device with the same 60 kJ energy input. In addition, FF-1 produced a new single-shot record of 240 ± 20 keV for mean ion energy, a record for any confined fusion plasma, using any device, and a 50% improvement in ten-shot mean ion energy. With a deuterium-nitrogen mix and corona-discharge pre-ionization, we were also able to reduce the standard deviation in the fusion yield to about 15%, a four-fold reduction over the copper-electrode results. We intend to further reduce impurities with new experiments using microwave treatment of tungsten electrodes, followed by the use of beryllium electrodes.

Liquid-purity monitor for the LUX-ZEPLIN dark matter search

NASA Astrophysics Data System (ADS)

Manalaysay, Aaron; Lux-Zeplin Collaboration

2016-03-01

The LUX-ZEPLIN (LZ) experiment will be the first liquid-xenon (LXe) dark matter search to feature a multi-tonne fiducial target. Drawing on the lessons learned in the LUX and ZEPLIN experiments, this next step will probe dark-matter candidates with unprecedented sensitivity. As these LXe detectors have grown larger, so too has the distance over which ionization electrons (from particle interactions) must be drifted through the liquid. Because of this, even minute levels of electronegative impurities can significantly attenuate the ionization signal, and must therefore be closely monitored. I will present the concept of a liquid-purity monitor which uses new and novel techniques, including state-of-the-art UV LEDs and low-work-function materials, and will measure levels of impurities in LZ's liquid circulation line in real time. This device will provide vital supplemental data to the roughly weekly in-situ purity measurements carried out within the detector's active volume, will greatly improve the resolution of the ionization channel in this detector, and will yield instant feedback in response to changing detector conditions.

Evaluation of computational models and cross sections used by MCNP6 for simulation of characteristic X-ray emission from thick targets bombarded by kiloelectronvolt electrons

NASA Astrophysics Data System (ADS)

Poškus, A.

2016-09-01

This paper evaluates the accuracy of the single-event (SE) and condensed-history (CH) models of electron transport in MCNP6.1 when simulating characteristic Kα, total K (=Kα + Kβ) and Lα X-ray emission from thick targets bombarded by electrons with energies from 5 keV to 30 keV. It is shown that the MCNP6.1 implementation of the CH model for the K-shell impact ionization leads to underestimation of the K yield by 40% or more for the elements with atomic numbers Z < 15 and overestimation of the Kα yield by more than 40% for the elements with Z > 25. The Lα yields are underestimated by more than an order of magnitude in CH mode, because MCNP6.1 neglects X-ray emission caused by electron-impact ionization of L, M and higher shells in CH mode (the Lα yields calculated in CH mode reflect only X-ray fluorescence, which is mainly caused by photoelectric absorption of bremsstrahlung photons). The X-ray yields calculated by MCNP6.1 in SE mode (using ENDF/B-VII.1 library data) are more accurate: the differences of the calculated and experimental K yields are within the experimental uncertainties for the elements C, Al and Si, and the calculated Kα yields are typically underestimated by (20-30)% for the elements with Z > 25, whereas the Lα yields are underestimated by (60-70)% for the elements with Z > 49. It is also shown that agreement of the experimental X-ray yields with those calculated in SE mode is additionally improved by replacing the ENDF/B inner-shell electron-impact ionization cross sections with the set of cross sections obtained from the distorted-wave Born approximation (DWBA), which are also used in the PENELOPE code system. The latter replacement causes a decrease of the average relative difference of the experimental X-ray yields and the simulation results obtained in SE mode to approximately 10%, which is similar to accuracy achieved with PENELOPE. This confirms that the DWBA inner-shell impact ionization cross sections are significantly more accurate than the corresponding ENDF/B cross sections when energy of incident electrons is of the order of the binding energy.

Computational Model of D-Region Ion Production Caused by Energetic Electron Precipitations Based on General Monte Carlo Transport Calculations

NASA Astrophysics Data System (ADS)

Kouznetsov, A.; Cully, C. M.

2017-12-01

During enhanced magnetic activities, large ejections of energetic electrons from radiation belts are deposited in the upper polar atmosphere where they play important roles in its physical and chemical processes, including VLF signals subionospheric propagation. Electron deposition can affect D-Region ionization, which are estimated based on ionization rates derived from energy depositions. We present a model of D-region ion production caused by an arbitrary (in energy and pitch angle) distribution of fast (10 keV - 1 MeV) electrons. The model relies on a set of pre-calculated results obtained using a general Monte Carlo approach with the latest version of the MCNP6 (Monte Carlo N-Particle) code for the explicit electron tracking in magnetic fields. By expressing those results using the ionization yield functions, the pre-calculated results are extended to cover arbitrary magnetic field inclinations and atmospheric density profiles, allowing ionization rate altitude profile computations in the range of 20 and 200 km at any geographic point of interest and date/time by adopting results from an external atmospheric density model (e.g. NRLMSISE-00). The pre-calculated MCNP6 results are stored in a CDF (Common Data Format) file, and IDL routines library is written to provide an end-user interface to the model.

Atomic kinetics of a neon photoionized plasma experiment at Z

NASA Astrophysics Data System (ADS)

Mayes, Daniel C.; Mancini, Roberto; Bailey, James E.; Loisel, Guillaume; Rochau, Gregory; ZAPP Collaboration

2018-06-01

We discuss an experimental effort to study the atomic kinetics in astrophysically relevant photoionized plasmas via K-shell line absorption spectroscopy. The experiment employs the intense x-ray flux emitted at the collapse of a Z-pinch to heat and backlight a photoionized plasma contained within a cm-scale gas cell placed at a variable distance from the Z-pinch and filled with neon gas pressures in the range from 3.5 to 30 Torr. The experimental platform affords an order of magnitude range in the ionization parameter characterizing the photoionized plasma at the peak of the x-ray drive from about 5 to 80 erg*cm/s. Thus, the experiment allows for the study of trends in ionization distribution as a function of the ionization parameter. An x-ray crystal spectrometer capable of time-integrated and/or time-gated configurations is used to collect absorption spectra. The spectra show line absorption by several ionization stages of neon, including Be-, Li-, He-, and H-like ions. Analysis of these spectra yields ion areal densities and charge state distributions, which can be compared with simulation results from atomic kinetics codes. In addition, the electron temperature is extracted from level population ratios of nearby energy levels in Li- and Be-like ions, which can be used to test heating models of photoionized plasmas.

Laser desorption ionization of small molecules assisted by tungsten oxide and rhenium oxide particles.

PubMed

Bernier, Matthew C; Wysocki, Vicki H; Dagan, Shai

2015-07-01

Inorganic metal oxides have shown potential as matrices for assisting in laser desorption ionization with advantages over the aromatic acids typically used. Rhenium and tungsten oxides are attractive options due to their high work functions and relative chemical inertness. In this work, it is shown that ReO3 and WO3 , in microparticle (μP) powder forms, can efficiently facilitate ionization of various types of small molecules and provide minimized background contamination at analyte concentrations below 1 ng/µL. This study shows that untreated inorganic WO3 and ReO3 particles are valid matrix options for detection of protonatable, radical, and precharged species under laser desorption ionization. Qualitatively, the WO3 μP showed improved detection of apigenin, sodiated glucose, and precharged analyte choline, while the ReO3 μP allowed better detection of protonated cocaine, quinuclidine, ametryn, and radical ions of polyaromatic hydrocarbons at detection levels as low as 50 pg/µL. For thermometer ion survival yield experiments, it was also shown that the ReO3 powder was significantly softer than α-cyano-4-hydroxycinnaminic acid. Furthermore, it provided higher intensities of cocaine and polyaromatic hydrocarbons, at laser flux values equal to those used with α-cyano-4-hydroxycinnaminic acid. Copyright © 2015 John Wiley & Sons, Ltd.

Effects of the Carrier-Envelope Phase in the Multiphoton Ionization Regime

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

Nakajima, Takashi; Institute for Solid State Physics, University of Tokyo, 5-1-5 Kashiwanoha, Kashiwa, Chiba 277-8581; Watanabe, Shuntaro

2006-06-02

We theoretically investigate the effects of the carrier-envelope phase of few-cycle laser pulses in the multiphoton ionization regime. For atoms with low ionization potential, total ionization yield barely exhibits phase dependence, as expected. However, population of some bound states clearly shows phase dependence. This implies that the measurement of the carrier-envelope phase would be possible through the photoemission between bound states without energy-and-angle-resolved photoelectron detection. The considered scheme could be particularly useful to measure the carrier-envelope phase for a light source without an amplifier, such as a laser oscillator, which cannot provide sufficient pulse energy to induce tunneling ionization.

Tailored nanopost arrays (NAPA) for laser desorption ionization in mass spectrometry

DOEpatents

Vertes, Akos; Walker, Bennett N.; Stolee, Jessica A.; Retterer, Scott T.

2016-11-08

The production and use of semiconducting nanopost arrays made by nanofabrication is described herein. These nanopost arrays (NAPA) provide improved laser ionization yields and controllable fragmentation with switching or modulation capabilities for mass spectrometric detection and identification of samples deposited on them.

Relative L-shell X-ray intensities of Pt, Pb and Bi following ionization by 59.54 keV γ-rays

NASA Astrophysics Data System (ADS)

Dhal, B. B.; Padhi, H. C.

1994-12-01

Relative L-shell X-ray intensities of Pt, Pb and Bi have been measured following ionization by 59.54 keV photons from an 241 Am point source. The measured ratios have been compared with the theoretical ratios estimated using the photoionization cross-sections of Scofield and different decay yield data. The comparison shows good agreement for Pb and Bi with the decay yield data of Krause, but the decay yield data of Xu and Xu overestimates the ratios, particularly for the {I γ}/{I α} ratio. Our results for Pb and Bi with improved error limits also agree with the previous experimental results of Shatendra et al. For Pt our present results are found to lie between the two theoretical results obtained by using different sets of decay yield data.

Experimental investigation of strong-field-ionization theories for laser fields from visible to midinfrared frequencies

NASA Astrophysics Data System (ADS)

Lai, Yu Hang; Xu, Junliang; Szafruga, Urszula B.; Talbert, Bradford K.; Gong, Xiaowei; Zhang, Kaikai; Fuest, Harald; Kling, Matthias F.; Blaga, Cosmin I.; Agostini, Pierre; DiMauro, Louis F.

2017-12-01

Strong-field-ionization yield versus intensity is investigated for various atomic targets (Ne, Ar, Kr, Xe, Na, K, Zn, and Mg) and light polarization from visible to mid-infrared (0.4-4 μ m ), from multiphoton to tunneling regimes. The experimental findings (normalized yield vs intensity, ratio of circular to linear polarization and saturation intensities) are compared to the theoretical models of Perelomov-Popov-Terent'ev (PPT) and Ammosov-Delone-Krainov (ADK). While PPT is generally satisfactory, ADK validity is found, as expected, to be much more limited.

Angle-dependent strong-field molecular ionization rates with tuned range-separated time-dependent density functional theory.

PubMed

Sissay, Adonay; Abanador, Paul; Mauger, François; Gaarde, Mette; Schafer, Kenneth J; Lopata, Kenneth

2016-09-07

Strong-field ionization and the resulting electronic dynamics are important for a range of processes such as high harmonic generation, photodamage, charge resonance enhanced ionization, and ionization-triggered charge migration. Modeling ionization dynamics in molecular systems from first-principles can be challenging due to the large spatial extent of the wavefunction which stresses the accuracy of basis sets, and the intense fields which require non-perturbative time-dependent electronic structure methods. In this paper, we develop a time-dependent density functional theory approach which uses a Gaussian-type orbital (GTO) basis set to capture strong-field ionization rates and dynamics in atoms and small molecules. This involves propagating the electronic density matrix in time with a time-dependent laser potential and a spatial non-Hermitian complex absorbing potential which is projected onto an atom-centered basis set to remove ionized charge from the simulation. For the density functional theory (DFT) functional we use a tuned range-separated functional LC-PBE*, which has the correct asymptotic 1/r form of the potential and a reduced delocalization error compared to traditional DFT functionals. Ionization rates are computed for hydrogen, molecular nitrogen, and iodoacetylene under various field frequencies, intensities, and polarizations (angle-dependent ionization), and the results are shown to quantitatively agree with time-dependent Schrödinger equation and strong-field approximation calculations. This tuned DFT with GTO method opens the door to predictive all-electron time-dependent density functional theory simulations of ionization and ionization-triggered dynamics in molecular systems using tuned range-separated hybrid functionals.

Angle-dependent strong-field molecular ionization rates with tuned range-separated time-dependent density functional theory

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

Sissay, Adonay; Abanador, Paul; Mauger, François

2016-09-07

Strong-field ionization and the resulting electronic dynamics are important for a range of processes such as high harmonic generation, photodamage, charge resonance enhanced ionization, and ionization-triggered charge migration. Modeling ionization dynamics in molecular systems from first-principles can be challenging due to the large spatial extent of the wavefunction which stresses the accuracy of basis sets, and the intense fields which require non-perturbative time-dependent electronic structure methods. In this paper, we develop a time-dependent density functional theory approach which uses a Gaussian-type orbital (GTO) basis set to capture strong-field ionization rates and dynamics in atoms and small molecules. This involves propagatingmore » the electronic density matrix in time with a time-dependent laser potential and a spatial non-Hermitian complex absorbing potential which is projected onto an atom-centered basis set to remove ionized charge from the simulation. For the density functional theory (DFT) functional we use a tuned range-separated functional LC-PBE*, which has the correct asymptotic 1/r form of the potential and a reduced delocalization error compared to traditional DFT functionals. Ionization rates are computed for hydrogen, molecular nitrogen, and iodoacetylene under various field frequencies, intensities, and polarizations (angle-dependent ionization), and the results are shown to quantitatively agree with time-dependent Schrödinger equation and strong-field approximation calculations. This tuned DFT with GTO method opens the door to predictive all-electron time-dependent density functional theory simulations of ionization and ionization-triggered dynamics in molecular systems using tuned range-separated hybrid functionals.« less

LASER DESORPTION/IONIZATION OF SINGLE ULTRAFINE MULTICOMPONENT AEROSOLS. (R823980)

EPA Science Inventory

Laser desorption/ionization characteristics of single
ultrafine multicomponent aerosols have been investigated.
The results confirm earlier findings that (a) the negative
ion spectra are dominated by free electrons and (b) the ion
yield-to-mass ratio is higher for ...

VUV PHOTO-PROCESSING OF PAH CATIONS: QUANTITATIVE STUDY ON THE IONIZATION VERSUS FRAGMENTATION PROCESSES

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

Zhen, Junfeng; Castillo, Sarah Rodriguez; Joblin, Christine

2016-05-10

Interstellar polycyclic aromatic hydrocarbons (PAHs) are strongly affected by the absorption of vacuum ultraviolet (VUV) photons in the interstellar medium (ISM), yet the branching ratio between ionization and fragmentation is poorly studied. This is crucial for the stability and charge state of PAHs in the ISM in different environments, affecting in turn the chemistry, the energy balance, and the contribution of PAHs to the extinction and emission curves. We studied the interaction of PAH cations with VUV photons in the 7–20 eV range from the synchrotron SOLEIL beamline, DESIRS. We recorded by action spectroscopy the relative intensities of photo-fragmentation andmore » photo-ionization for a set of eight PAH cations ranging in size from 14 to 24 carbon atoms, with different structures. At photon energies below ∼13.6 eV fragmentation dominates for the smaller species, while for larger species ionization is immediately competitive after the second ionization potential (IP). At higher photon energies all species behave similarly; the ionization yield gradually increases, leveling off between 0.8 and 0.9 at ∼18 eV. Among isomers, PAH structure appears to mainly affect the fragmentation cross section but not the ionization cross section. We also measured the second IP for all species and the third IP for two of them; all are in good agreement with theoretical ones, confirming that PAH cations can be further ionized in the diffuse ISM. Determining actual PAH dication abundances in the ISM will require detailed modeling. Our measured photo-ionization yields for several PAH cations provide a necessary ingredient for such models.« less

Electron beam plasma ionizing target for the production of neutron-rich nuclides

NASA Astrophysics Data System (ADS)

Panteleev, V. N.; Barzakh, A. E.; Essabaa, S.; Fedorov, D. V.; Ionan, A. M.; Ivanov, V. S.; Lau, C.; Leroy, R.; Lhersonneau, G.; Mezilev, K. A.; Molkanov, P. L.; Moroz, F. V.; Orlov, S. Yu.; Stroe, L.; Tecchio, L. B.; Villari, A. C. C.; Volkov, Yu. M.

2008-10-01

The production of neutron-rich Ag, In and Sn isotopes from a uranium carbide target of a high density has been investigated at the IRIS facility in the PLOG (PNPI-Legnaro-GANIL-Orsay) collaboration. The UC target material with a density of 12 g/cm3 was prepared by the method of powder metallurgy in a form of pellets of 2 mm thickness, 11 mm in diameter and grain dimensions of about 20 μm. The uranium target mass of 31 g was exposed at a 1 GeV proton beam of intensity 0.05-0.07 μA. For the ionization of the produced species the electron beam-plasma ionization inside the target container (ionizing target) has been used. It was the first experiment when the new high density UC target material was exploited with the electron-plasma ionization. Yields of Sn isotopes have been measured in the target temperature range of (1900-2100) °C. The yields of some Pd, In and Cd isotopes were measured as well to compare to previously measured ones from a high density uranium carbide target having a ceramic-like structure. For the first time a nickel isotope was obtained from a high density UC target.

Identification and clarification of the role of key active site residues in bacterial glutathione S-transferase zeta/maleylpyruvate isomerase

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

Fang, Ti; Li, De-Feng; Zhou, Ning-Yi, E-mail: n.zhou@pentium.whiov.ac.cn

2011-07-08

Highlights: {yields} Application of site-directed mutagenesis to probe the active site residues of glutathione-dependent maleylpyruvate isomerase. {yields} Two conserved residues, Arg8 and Arg176, in zeta class glutathione S-transferases are critical for maleylpyruvate orientation and enolization. {yields} Arg109, found exclusively in NagL, participates in k{sub cat} regulation. {yields} The T11A mutant exhibited a significantly decreased K{sub m} value for glutathione with little impact on maleylpyruvate kinetics. {yields} The Thr11 residue appears to have significance in the evolution of glutathione S-transferase classes. -- Abstract: The maleylpyruvate isomerase NagL from Ralstonia sp. strain U2, which has been structurally characterized previously, catalyzes the isomerizationmore » of maleylpyruvate to fumarylpyruvate. It belongs to the class zeta glutathione S-transferases (GSTZs), part of the cytosolic GST family (cGSTs). In this study, site-directed mutagenesis was conducted to probe the functions of 13 putative active site residues. Steady-state kinetic information for mutants in the reduced glutathione (GSH) binding site, suggested that (a) Gln64 and Asp102 interact directly with the glutamyl moiety of glutathione, (b) Gln49 and Gln64 are involved in a potential electron-sharing network that influences the ionization of the GSH thiol. The information also suggests that (c) His38, Asn108 and Arg109 interact with the GSH glycine moiety, (d) His104 has a role in the ionization of the GSH sulfur and the stabilization of the maleyl terminal carboxyl group in the reaction intermediate and (e) Arg110 influences the electron distribution in the active site and therefore the ionization of the GSH thiolate. Kinetic data for mutants altered in the substrate-binding site imply that (a) Arg8 and Arg176 are critical for maleylpyruvate orientation and enolization, and (b) Arg109 (exclusive to NagL) participates in k{sub cat} regulation. Surprisingly, the T11A mutant had a decreased GSH K{sub m} value, whereas little impact on maleylpyruvate kinetics was observed, suggesting that this residue plays an important role in GSH binding. An evolutionary trend in this residue appears to have developed not only in prokaryotic and eukaryotic GSTZs, but also among the wider class of cGSTs.« less

Recollision induced excitation-ionization with counter-rotating two-color circularly polarized laser field

NASA Astrophysics Data System (ADS)

Ben, Shuai; Guo, Pei-Ying; Pan, Xue-Fei; Xu, Tong-Tong; Song, Kai-Li; Liu, Xue-Shen

2017-07-01

Nonsequential double ionization of Ar by a counter-rotating two-color circularly polarized laser field is theoretically investigated. At the combined intensity in the "knee" structure range, the double ionization occurs mainly through recollision induced excitation followed by subsequent ionization of Ar+∗ . By tracing the history of the recollision trajectories, we explain how the relative intensity ratio of the two colors controls the correlated electron dynamics and optimizes the ionization yields. The major channels contributing to enhancing the double ionization are through the elliptical trajectories with smaller travel time but not through the triangle shape or the other long cycle trajectories. Furthermore, the correlated electron dynamics could be limited to the attosecond time scale by adjusting the relative intensity ratio. Finally, the double ionization from doubly excited complex at low laser intensity is qualitatively discussed.

Spectral synthesis in the ultraviolet. II - Stellar populations and star formation in blue compact galaxies

NASA Technical Reports Server (NTRS)

Fanelli, Michael N.; O'Connell, Robert W.; Thuan, Trinh X.

1988-01-01

An initial attempt to apply optimizing spectral synthesis techniques to the far-UV spectra of blue compact galaxies (BCGs) is presented. The far-UV absorption-line spectra of the galaxies are clearly composite, with the signatures of the main-sequence types between O3 and mid-A. Most of the low-ionization absorption lines have a stellar origin. The Si IV and C IV features in several objects have P Cygni profiles. In Haro I the strength of Si IV indicates a significant blue supergiant population. The metal-poor blue compact dwarf Mrk 209 displays weak absorption lines, evidence that the stellar component has the same low metallicity as observed in the ionized gas. Good fits to the data are obtained the technique of optimizing population synthesis. The solutions yield stellar luminosity functions which display large discontinuities, indicative of discrete star formation episodes or bursts. The amount of UV extinction is low.

Absolute total and partial dissociative cross sections of pyrimidine at electron and proton intermediate impact velocities

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

Wolff, Wania, E-mail: wania@if.ufrj.br; Luna, Hugo; Sigaud, Lucas

Absolute total non-dissociative and partial dissociative cross sections of pyrimidine were measured for electron impact energies ranging from 70 to 400 eV and for proton impact energies from 125 up to 2500 keV. MOs ionization induced by coulomb interaction were studied by measuring both ionization and partial dissociative cross sections through time of flight mass spectrometry and by obtaining the branching ratios for fragment formation via a model calculation based on the Born approximation. The partial yields and the absolute cross sections measured as a function of the energy combined with the model calculation proved to be a useful toolmore » to determine the vacancy population of the valence MOs from which several sets of fragment ions are produced. It was also a key point to distinguish the dissociation regimes induced by both particles. A comparison with previous experimental results is also presented.« less

Localizing high-lying Rydberg wave packets with two-color laser fields

NASA Astrophysics Data System (ADS)

Larimian, Seyedreza; Lemell, Christoph; Stummer, Vinzenz; Geng, Ji-Wei; Roither, Stefan; Kartashov, Daniil; Zhang, Li; Wang, Mu-Xue; Gong, Qihuang; Peng, Liang-You; Yoshida, Shuhei; Burgdörfer, Joachim; Baltuška, Andrius; Kitzler, Markus; Xie, Xinhua

2017-08-01

We demonstrate control over the localization of high-lying Rydberg wave packets in argon atoms with phase-locked orthogonally polarized two-color laser fields. With a reaction microscope, we measure ionization signals of high-lying Rydberg states induced by a weak dc field and blackbody radiation as a function of the relative phase between the two-color fields. We find that the dc-field-ionization yield of high-lying Rydberg argon atoms oscillates with the relative two-color phase with a period of 2 π while the photoionization signal by blackbody radiation shows a period of π . Accompanying simulations show that these observations are a clear signature of the asymmetric localization of electrons recaptured into very elongated (low angular momentum) high-lying Rydberg states after conclusion of the laser pulse. Our findings thus open an effective pathway to control the localization of high-lying Rydberg wave packets.

The galaxy NGC 1566 - Distribution and kinematics of the ionized gas

NASA Astrophysics Data System (ADS)

Comte, G.; Duquennoy, A.

1982-10-01

H-alpha narrowband observations are the basis of a study of ionized hydrogen in the large spiral galaxy NGC 1566 which has yielded a catalog of 418 H II regions covering the main body of the galaxy, supplemented by 59 positions and estimated H-alpha luminosities for regions located in the pseudo-outer ring where no H-alpha plate is available. A discussion of luminosity function, diameter distribution and spiral structure notes evidence for a double two-armed spiral pattern. The plane of the galaxy appears warped, and the efficiency of the two different spiral patterns in star formation is different. A preliminary radial velocity field is determined from three interferograms in H-alpha light, and is found to be acceptably fitted by a simple bulge-plus-disk dynamical model in which the apparent disk mass-to-light ratio sharply increases from center to edge.

UV Lamp as a Facile Ozone Source for Structural Analysis of Unsaturated Lipids Via Electrospray Ionization-Mass Spectrometry.

PubMed

Stinson, Craig A; Zhang, Wenpeng; Xia, Yu

2018-03-01

Ozonolysis of alkene functional groups is a type of highly specific and effective chemical reaction, which has found increasing applications in structural analysis of unsaturated lipids via coupling with mass spectrometry (MS). In this work, we utilized a low-pressure mercury lamp (6 W) to initiate ozonolysis inside electrospray ionization (ESI) sources. By placing the lamp near a nanoESI emitter that partially transmits 185 nm ultraviolet (UV) emission from the lamp, dissolved dioxygen in the spray solution was converted into ozone, which subsequently cleaved the double bonds within fatty acyls of lipids. Solvent conditions, such as presence of water and acid solution pH, were found to be critical in optimizing ozonolysis yields. Fast (on seconds time scale) and efficient (50%-100% yield) ozonolysis was achieved for model unsaturated phospholipids and fatty acids with UV lamp-induced ozonolysis incorporated on a static and an infusion nanoESI source. The method was able to differentiate double bond location isomers and identify the geometry of the double bond based on yield. The analytical utility of UV lamp-induced ozonolysis was further demonstrated by implementation on a liquid chromatography (LC)-MS platform. Ozonolysis was effected in a flow microreactor that was made from ozone permeable tubing, so that ambient ozone produced by the lamp irradiation could diffuse into the reactor and induce online ozonolysis post-LC separation and before ESI-MS. Graphical Abstract ᅟ.

UV Lamp as a Facile Ozone Source for Structural Analysis of Unsaturated Lipids Via Electrospray Ionization-Mass Spectrometry

NASA Astrophysics Data System (ADS)

Stinson, Craig A.; Zhang, Wenpeng; Xia, Yu

2018-03-01

Ozonolysis of alkene functional groups is a type of highly specific and effective chemical reaction, which has found increasing applications in structural analysis of unsaturated lipids via coupling with mass spectrometry (MS). In this work, we utilized a low-pressure mercury lamp (6 W) to initiate ozonolysis inside electrospray ionization (ESI) sources. By placing the lamp near a nanoESI emitter that partially transmits 185 nm ultraviolet (UV) emission from the lamp, dissolved dioxygen in the spray solution was converted into ozone, which subsequently cleaved the double bonds within fatty acyls of lipids. Solvent conditions, such as presence of water and acid solution pH, were found to be critical in optimizing ozonolysis yields. Fast (on seconds time scale) and efficient (50%-100% yield) ozonolysis was achieved for model unsaturated phospholipids and fatty acids with UV lamp-induced ozonolysis incorporated on a static and an infusion nanoESI source. The method was able to differentiate double bond location isomers and identify the geometry of the double bond based on yield. The analytical utility of UV lamp-induced ozonolysis was further demonstrated by implementation on a liquid chromatography (LC)-MS platform. Ozonolysis was effected in a flow microreactor that was made from ozone permeable tubing, so that ambient ozone produced by the lamp irradiation could diffuse into the reactor and induce online ozonolysis post-LC separation and before ESI-MS. [Figure not available: see fulltext.

Coherent control of strong-field two-pulse ionization of Rydberg atoms.

PubMed

Fedorov, M; Poluektov, N

2000-02-28

Strong-field ionization of Rydberg atoms is investigated in its dependence on phase features of the initial coherent population of Rydberg levels. In the case of a resonance between Rydberg levels and some lower-energy atomic level (V-type transitions), this dependence is shown to be very strong: by a proper choice of the initial population an atom can be made either completely or very little ionized by a strong laser pulse. It is shown that phase features of the initial coherent population of Rydberg levels and the ionization yield can be efficiently controlled in a scheme of ionization by two strong laser pulses with a varying delay time between them.

Multiple ionization of C 60 in collisions with 2.33 MeV/u O-ions and giant plasmon excitation

NASA Astrophysics Data System (ADS)

Kelkar, A. H.; Kadhane, U.; Misra, D.; Kumar, Ajay; Tribedi, L. C.

2007-03-01

Single and multiple ionization of C60 in collisions with fast (v = 9.7 a.u.) Oq+ ions have been studied. Relative cross sections for production of C 601+ to C 604+ have been measured. The intensity ratios of double-to-single ionization agree very well with a model based on giant dipole plasmon resonance (GDPR). Almost linear increasing trend of the yields of single and double ionizations with projectile charge state is well reproduced by the single and double plasmon excitation mechanisms. The observed charge state independence of triple and quadruple ionization is in sharp contrast to the GDPR model.

Extreme ultraviolet photoionization of aldoses and ketoses

NASA Astrophysics Data System (ADS)

Shin, Joong-Won; Dong, Feng; Grisham, Michael E.; Rocca, Jorge J.; Bernstein, Elliot R.

2011-04-01

Gas phase monosaccharides (2-deoxyribose, ribose, arabinose, xylose, lyxose, glucose galactose, fructose, and tagatose), generated by laser desorption of solid sample pellets, are ionized with extreme ultraviolet photons (EUV, 46.9 nm, 26.44 eV). The resulting fragment ions are analyzed using a time of flight mass spectrometer. All aldoses yield identical fragment ions regardless of size, and ketoses, while also generating same ions as aldoses, yields additional features. Extensive fragmentation of the monosaccharides is the result the EUV photons ionizing various inner valence orbitals. The observed fragmentation patterns are not dependent upon hydrogen bonding structure or OH group orientation.

Resonant ionization spectroscopy of autoionizing Rydberg states in cobalt and redetermination of its ionization potential

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

Liu, Yuan; Gottwald, T.; Mattolat, C.

We obtained multi-step resonance ionization spectroscopy of cobalt using a hot-cavity laser ion source and three Ti:Sapphire lasers. Furthermore, the photoionization spectra revealed members of five new autoionizing Rydberg series that originate from three different lower levels of 3d 74s5s h 4F 9/2, 3d 74s4d f 4G 11/2, and 3d 74s4d f 4H 13/2 and converge to the first four excited states of singly ionized Co. Our analyses of the Rydberg series yield 63564.689 0.036 cm -1 as the first ionization potential of Co, which is an order of magnitude more accurate than the previous estimation. Using a three-step resonancemore » ionization scheme that employs an autoinizing Rydberg state in the last transition, we obtained an overall ionization efficiency of about 18% for Co.« less

Resonant ionization spectroscopy of autoionizing Rydberg states in cobalt and redetermination of its ionization potential

DOE PAGES

Liu, Yuan; Gottwald, T.; Mattolat, C.; ...

2017-03-20

We obtained multi-step resonance ionization spectroscopy of cobalt using a hot-cavity laser ion source and three Ti:Sapphire lasers. Furthermore, the photoionization spectra revealed members of five new autoionizing Rydberg series that originate from three different lower levels of 3d 74s5s h 4F 9/2, 3d 74s4d f 4G 11/2, and 3d 74s4d f 4H 13/2 and converge to the first four excited states of singly ionized Co. Our analyses of the Rydberg series yield 63564.689 0.036 cm -1 as the first ionization potential of Co, which is an order of magnitude more accurate than the previous estimation. Using a three-step resonancemore » ionization scheme that employs an autoinizing Rydberg state in the last transition, we obtained an overall ionization efficiency of about 18% for Co.« less

A Radiation Chemistry Code Based on the Greens Functions of the Diffusion Equation

NASA Technical Reports Server (NTRS)

Plante, Ianik; Wu, Honglu

2014-01-01

Ionizing radiation produces several radiolytic species such as.OH, e-aq, and H. when interacting with biological matter. Following their creation, radiolytic species diffuse and chemically react with biological molecules such as DNA. Despite years of research, many questions on the DNA damage by ionizing radiation remains, notably on the indirect effect, i.e. the damage resulting from the reactions of the radiolytic species with DNA. To simulate DNA damage by ionizing radiation, we are developing a step-by-step radiation chemistry code that is based on the Green's functions of the diffusion equation (GFDE), which is able to follow the trajectories of all particles and their reactions with time. In the recent years, simulations based on the GFDE have been used extensively in biochemistry, notably to simulate biochemical networks in time and space and are often used as the "gold standard" to validate diffusion-reaction theories. The exact GFDE for partially diffusion-controlled reactions is difficult to use because of its complex form. Therefore, the radial Green's function, which is much simpler, is often used. Hence, much effort has been devoted to the sampling of the radial Green's functions, for which we have developed a sampling algorithm This algorithm only yields the inter-particle distance vector length after a time step; the sampling of the deviation angle of the inter-particle vector is not taken into consideration. In this work, we show that the radial distribution is predicted by the exact radial Green's function. We also use a technique developed by Clifford et al. to generate the inter-particle vector deviation angles, knowing the inter-particle vector length before and after a time step. The results are compared with those predicted by the exact GFDE and by the analytical angular functions for free diffusion. This first step in the creation of the radiation chemistry code should help the understanding of the contribution of the indirect effect in the formation of DNA damage and double-strand breaks.

High harmonic generation at the tunneling ionization of atoms by intense laser radiation near the classical cut-off

NASA Astrophysics Data System (ADS)

Gets, A. V.; Krainov, V. P.

2018-01-01

The yield of spontaneous photons at the tunneling ionization of atoms by intense low-frequency laser radiation near the classical cut-off is estimated analytically by using the three-step model. The Bell-shaped dependence in the universal photon spectrum is explained qualitatively.

Solar coronal temperature diagnostics using emission line from multiple stages of ionization of iron

NASA Technical Reports Server (NTRS)

Brosius, Jeffrey W.; Davila, Joseph M.; Thomas, Roger J.; Thompson, William T.

1994-01-01

We obtained spatially resolved extreme-ultraviolet (EUV) spectra of AR 6615 on 1991 May 7 with NASA/ Goddard Space Flight Center's Solar EUV Rocket Telescope and Spectrograph (SERTS). Included are emission lines from four different stages of ionization of iron: Fe(+15) lambda 335 A, Fe(+14) lambda 327 A, Fe(+13) lambda 334 A, and Fe(+12) lambda 348 A. Using intensity ratios from among these lines, we have calculated the active region coronal temperature along the Solar Extreme Ultraviolet Telescope and Spectrograph (SERTS) slit. Temperatures derived from line ratios which incorporate adjacent stages of ionization are most sensitive to measurement uncertainties and yield the largest scatter. Temperatures derived from line ratios which incorporate nonadjacent stages of ionization are less sensitive to measurement uncertainties and yield little scatter. The active region temperature derived from these latter ratios has an average value of 2.54 x 10(exp 6) K, with a standard deviation approximately 0.12 x 10(exp 6) K, and shows no significant variation with position along the slit.

Quantitative measurements of vaporization, burst ionization, and emission characteristics of shaped charge barium releases

NASA Technical Reports Server (NTRS)

Hoch, Edward L.; Hallinan, Thomas J.; Stenbaek-Nielsen, Hans C.

1994-01-01

Intensity-calibrated color video recordings of three barium-shaped charge injections in the ionopshere were used to determine the initial ionization, the column density corresponding to unity optical depth, and the yield of vaporized barium in the fast jet. It was found that the initial ionization at the burst was less than 1% and that 0% burst ionization was consistent with the observations. Owing to the Doppler shift, the column density for optical thickness in the neutral barium varies somewhat according to the velocity distribution. For the cases examined here, the column density was 2-5 x 10(exp 10) atoms/sq cm. This value, which occurred 12 to 15 s after release, should be approximately valid for most shaped charge experiments. The yield was near 30% (15% in the fast jet) for two of the releases and was somewhat lower in the third, which also had a lower peak velocity. This study also demonstrated the applicability of the computer simulation code developed for chemical releases by Stenbaek-Nielsen and provided experimental verification of the Doppler-corrected emission rates calculated b Stenbaek-Nielsen (1989).

The effects of pre-ionization on the impurity and x-ray level in a dense plasma focus device

NASA Astrophysics Data System (ADS)

Piriaei, D.; Yousefi, H. R.; Mahabadi, T. D.; Salar Elahi, A.; Ghoranneviss, M.

2017-02-01

In this study, the effects of pre-ionization on the reduction of the impurities and non-uniformities, the increased stability of the pinch plasma, the enhancement of the total hard x-ray yield, the plasmoid x-ray yield, and the current sheath dynamics of the argon gas at different pressures in a Mather type plasma focus device were investigated. For this purpose, different shunt resistors together with two x-ray detectors were used, and the data gathered from the x-ray signals showed that the optimum shunt resistor could cause the maximum total hard and plasmoid hard x-ray emissions. Moreover, in order to calculate the average speed of the current sheath, two axial magnetic probes were used. It was revealed that the pre-ionization could increase the whole range of the emitted x-rays and produce a more uniform current sheath layer, which moved faster, and this technique could lead to the reduction of the impurities, creating a more stabilized pinched plasma, which was capable of emitting more x-rays than the usual case without using pre-ionization.

Statistical analysis of fragmentation patterns of electron ionization mass spectra of enolized-trimethylsilylated anabolic androgenic steroids

NASA Astrophysics Data System (ADS)

Fragkaki, A. G.; Angelis, Y. S.; Tsantili-Kakoulidou, A.; Koupparis, M.; Georgakopoulos, C.

2009-08-01

Anabolic androgenic steroids (AAS) are included in the List of prohibited substances of the World Anti-Doping Agency (WADA) as substances abused to enhance athletic performance. Gas chromatography coupled to mass spectrometry (GC-MS) plays an important role in doping control analyses identifying AAS as their enolized-trimethylsilyl (TMS)-derivatives using the electron ionization (EI) mode. This paper explores the suitability of complementary GC-MS mass spectra and statistical analysis (principal component analysis, PCA and partial least squares-discriminant analysis, PLS-DA) to differentiate AAS as a function of their structural and conformational features expressed by their fragment ions. The results obtained showed that the application of PCA yielded a classification among the AAS molecules which became more apparent after applying PLS-DA to the dataset. The application of PLS-DA yielded a clear separation among the AAS molecules which were, thus, classified as: 1-ene-3-keto, 3-hydroxyl with saturated A-ring, 1-ene-3-hydroxyl, 4-ene-3-keto, 1,4-diene-3-keto and 3-keto with saturated A-ring anabolic steroids. The study of this paper also presents structurally diagnostic fragment ions and dissociation routes providing evidence for the presence of unknown AAS or chemically modified molecules known as designer steroids.

Atomic kinetics of a neon photoionized plasma experiment at Z

NASA Astrophysics Data System (ADS)

Mayes, D. C.; Mancini, R. C.; Schoenfeld, R. P.; Bailey, J. E.; Loisel, G. P.; Rochau, G. A.; ZAPP Collaboration

2017-10-01

We discuss an experimental effort to study the atomic kinetics in neon photoionized plasmas via K-shell line absorption spectroscopy. The experiment employs the intense x-ray flux emitted at the collapse of a Z-pinch to heat and backlight a photoionized plasma contained within a cm-scale gas cell placed at various distances from the Z-pinch and filled with neon gas pressures in the range from 3.5 to 120 Torr. The experimental platform affords an order of magnitude range in the ionization parameter characterizing the photoionized plasma from about 5 to 80 erg*cm/s. Thus, the experiment allows for the study of trends in ionization distribution as a function of the ionization parameter. An x-ray crystal spectrometer capable of collecting both time-integrated and time-gated data is used to collect absorption spectra. The spectra show line absorption by several ionization stages of neon, including Be-, Li-, He-, and H-like ions. Analysis of these spectra yields ion areal-densities and charge state distributions, which can be compared with results from atomic kinetics codes. In addition, the electron temperature is extracted from level population ratios of nearby energy levels in Li- and Be-like ions, which can be used to test heating models of photoionized plasmas. This work was sponsored in part by DOE Office of Science Grant DE-SC0014451, and the Z Facility Fundamental Science Program of SNL.

Direct computation of general chemical energy differences: Application to ionization potentials, excitation, and bond energies.

PubMed

Beste, A; Harrison, R J; Yanai, T

2006-08-21

Chemists are mainly interested in energy differences. In contrast, most quantum chemical methods yield the total energy which is a large number compared to the difference and has therefore to be computed to a higher relative precision than would be necessary for the difference alone. Hence, it is desirable to compute energy differences directly, thereby avoiding the precision problem. Whenever it is possible to find a parameter which transforms smoothly from an initial to a final state, the energy difference can be obtained by integrating the energy derivative with respect to that parameter (cf. thermodynamic integration or adiabatic connection methods). If the dependence on the parameter is predominantly linear, accurate results can be obtained by single-point integration. In density functional theory and Hartree-Fock, we applied the formalism to ionization potentials, excitation energies, and chemical bond breaking. Example calculations for ionization potentials and excitation energies showed that accurate results could be obtained with a linear estimate. For breaking bonds, we introduce a nongeometrical parameter which gradually turns the interaction between two fragments of a molecule on. The interaction changes the potentials used to determine the orbitals as well as the constraint on the orbitals to be orthogonal.

Laser Desorption Ionization of small molecules assisted by Tungsten oxide and Rhenium oxide particles

PubMed Central

Bernier, Matthew; Wysocki, Vicki; Dagan, Shai

2015-01-01

Inorganic metal oxides have shown potential as matrices for assisting in laser desorption ionization (LDI) with advantages over the aromatic acids typically used. Rhenium and tungsten oxides are an attractive option due to their high work functions and relative chemical inertness. In this work, it is shown that ReO3 and WO3, in microparticle (μP) powder forms, can efficiently ionize various types of small molecules and provide minimized background contamination at analyte concentrations below 1 ng/μL. This study shows that untreated inorganic WO3 and ReO3 particles are valid matrix options for detection of protonatable, radical, and precharged species under LDI. Qualitatively, the WO3 μP showed an improved detection of apigenin, sodiated glucose, and the precharged analyte choline, while the ReO3 μP allowed detection of protonated cocaine, quinuclidine, ametryn, and radical ions of polyaromatic hydrocarbons at detection levels as low as 50 pg/μL. For thermometer ion survival yield experiments, it was also shown that the ReO3 powder was significantly softer than CCA. Furthermore, it provided higher intensities of cocaine and polyaromatic hydrocarbons, at laser flux values equal to that used with CCA. PMID:26349643

Ghost peaks observed after AP-MALDI experiment may disclose new ionization mechanism of matrix assisted hypersonic velocity impact ionization

PubMed Central

Moskovets, Eugene

2015-01-01

RATIONALE Understanding the mechanisms of MALDI promises improvements in the sensitivity and specificity of many established applications in the field of mass spectrometry. This paper reports a serendipitous observation of a significant ion yield in a post-ionization experiment conducted after the sample has been removed from a standard atmospheric pressure (AP)-MALDI source. This post-ionization is interpreted in terms of collisions of microparticles moving with a hypersonic velocity into a solid surface. Calculations show that the thermal energy released during such collisions is close to that absorbed by the top matrix layer in traditional MALDI. The microparticles, containing both the matrix and analytes, could be detached from a film produced inside the inlet capillary during the sample ablation and accelerated by the flow rushing through the capillary. These observations contribute some new perspective to ion formation in both laser and laserless matrix-assisted ionization. METHODS An AP-MALDI ion source hyphenated with a three-stage high-pressure ion funnel system was utilized for peptide mass analysis. After the laser was turned off and MALDI sample was removed, ions were detected during a gradual reduction of the background pressure in the first funnel. The constant-rate pressure reduction led to the reproducible appearance of different singly- and doubly-charged peptide peaks in mass spectra taken a few seconds after the end of the MALDI analysis of a dried-droplet spot. RESULTS The ion yield as well as the mass range of ions observed with a significant delay after a completion of the primary MALDI analysis depended primarily on the background pressure inside the first funnel. The production of ions in this post-ionization step was exclusively observed during the pressure drop. A lower matrix background and significant increase in relative yield of double-protonated ions are reported. CONCLUSIONS The observations were partially consistent with a model of the supersonic jet from the inlet capillary accelerating detached particles to kinetic energies suitable for matrix-assisted hypersonic-velocity impact ionization. PMID:26212165

Real-Time Food Authentication Using a Miniature Mass Spectrometer.

PubMed

Gerbig, Stefanie; Neese, Stephan; Penner, Alexander; Spengler, Bernhard; Schulz, Sabine

2017-10-17

Food adulteration is a threat to public health and the economy. In order to determine food adulteration efficiently, rapid and easy-to-use on-site analytical methods are needed. In this study, a miniaturized mass spectrometer in combination with three ambient ionization methods was used for food authentication. The chemical fingerprints of three milk types, five fish species, and two coffee types were measured using electrospray ionization, desorption electrospray ionization, and low temperature plasma ionization. Minimum sample preparation was needed for the analysis of liquid and solid food samples. Mass spectrometric data was processed using the laboratory-built software MS food classifier, which allows for the definition of specific food profiles from reference data sets using multivariate statistical methods and the subsequent classification of unknown data. Applicability of the obtained mass spectrometric fingerprints for food authentication was evaluated using different data processing methods, leave-10%-out cross-validation, and real-time classification of new data. Classification accuracy of 100% was achieved for the differentiation of milk types and fish species, and a classification accuracy of 96.4% was achieved for coffee types in cross-validation experiments. Measurement of two milk mixtures yielded correct classification of >94%. For real-time classification, the accuracies were comparable. Functionality of the software program and its performance is described. Processing time for a reference data set and a newly acquired spectrum was found to be 12 s and 2 s, respectively. These proof-of-principle experiments show that the combination of a miniaturized mass spectrometer, ambient ionization, and statistical analysis is suitable for on-site real-time food authentication.

Photoionization and ionic dissociation of the C3 H3 NS molecule induced by soft X-ray near the C1s edge.

PubMed

Lago, A F; Januário, R D; Cavasso Filho, R L; Simon, M; Dávalos, J Z

2017-10-01

Time of flight mass spectrometry, electron-ion coincidence, and ion yield spectroscopy were employed to investigate for the first time the thiazole (C 3 H 3 NS) molecule in the gas phase excited by synchrotron radiation in the soft X-ray domain. Total ion yield (TIY) and photoelectron-photoion coincidence (PEPICO) spectra were recorded as a function of the photon energy in the vicinity of the carbon K edge (C1s). The C1s resonant transitions as well as the core ionization thresholds have been determined from the profile of TIY spectrum, and the features were discussed. The corresponding partial ion yields were determined from the PEPICO spectra for the cation species produced upon the molecular photodissociation. Additional ab initio calculations have also been performed from where relevant structural and electronic configuration parameters were obtained for this molecule. Copyright © 2017 John Wiley & Sons, Ltd.

Luminescence of water or ice as a new detection method for magnetic monopoles

NASA Astrophysics Data System (ADS)

Pollmann, Anna Obertacke

2017-12-01

Cosmic ray detectors use air as a radiator for luminescence. In water and ice, Cherenkov light is the dominant light producing mechanism when the particle's velocity exceeds the Cherenkov threshold, approximately three quarters of the speed of light in vacuum. Luminescence is produced by highly ionizing particles passing through matter due to the electronic excitation of the surrounding molecules. The observables of luminescence, such as the wavelength spectrum and decay times, are highly dependent on the properties of the medium, in particular, temperature and purity. The results for the light yield of luminescence of previous measurements vary by two orders of magnitude. It will be shown that even for the lowest measured light yield, luminescence is an important signature of highly ionizing particles below the Cherenkov threshold. These could be magnetic monopoles or other massive and highly ionizing exotic particles. With the highest observed efficiencies, luminescence may even contribute significantly to the light output of standard model particles such as the PeV IceCube neutrinos. We present analysis techniques to use luminescence in neutrino telescopes and discuss experimental setups to measure the light yield of luminescence for the particular conditions in neutrino detectors.

An equation for the prediction of human skin permeability of neutral molecules, ions and ionic species.

PubMed

Zhang, Keda; Abraham, Michael H; Liu, Xiangli

2017-04-15

Experimental values of permeability coefficients, as log K p , of chemical compounds across human skin were collected by carefully screening the literature, and adjusted to 37°C for the effect of temperature. The values of log K p for partially ionized acids and bases were separated into those for their neutral and ionic species, forming a total data set of 247 compounds and species (including 35 ionic species). The obtained log K p values have been regressed against Abraham solute descriptors to yield a correlation equation with R 2 =0.866 and SD=0.432 log units. The equation can provide valid predictions for log K p of neutral molecules, ions and ionic species, with predictive R 2 =0.858 and predictive SD=0.445 log units calculated by the leave-one-out statistics. The predicted log K p values for Na + and Et 4 N + are in good agreement with the observed values. We calculated the values of log K p of ketoprofen as a function of the pH of the donor solution, and found that log K p markedly varies only when ketoprofen is largely ionized. This explains why models that neglect ionization of permeants still yield reasonable statistical results. The effect of skin thickness on log K p was investigated by inclusion of two indicator variables, one for intermediate thickness skin and one for full thickness skin, into the above equation. The newly obtained equations were found to be statistically very close to the above equation. Therefore, the thickness of human skin used makes little difference to the experimental values of log K p . Copyright © 2017 Elsevier B.V. All rights reserved.

Energy Dependence of Fission Product Yields from 235 U, 238U, and 239Pu for Incident Neutron Energies Between 0.5 and 14.8 MeV

NASA Astrophysics Data System (ADS)

Gooden, Matthew Edgell

A joint collaboration between the Triangle Universities Nuclear Laboratory (TUNL), Los Alamos National Laboratory (LANL) and Lawrence Livermore National Laboratory (LLNL) has performed a set of absolute Fission Product Yield (FPY) measurements. Using monoenergetic neutron at energies between 0.5 and 14.8 MeV, the excitation functions of a number of fission products from 235U, 238U and 239Pu have begun to be mapped out. This work has practical applications for the determination of weapon yields and the rate of burn-up in nuclear reactors, while also providing important insight into the fission process. Combining the use of a dual-fission ionization chamber and gamma-ray spectroscopy, absolute FPYs have been determined for approximately 15 different fission products. The dual-fission chamber is a back-to-back ionization chamber system with a 'thin' actinide foil in each chamber as a monitor or reference foil. The chamber holds a 'thick' target in the center of the system such that the target and reference foils are of the same actinide isotope. This allows for simple mass scaling between the recorded number of fissions in the individual chambers and the number of fissions in the center thick target, eliminating the need for the knowledge of the absolute fission cross section and its uncertainty. The 'thick' target was removed after activation and gamma-rays counted with well shielded High Purity Germanium (HPGe) detectors for a period of 1.5 - 2 months.

Manganese oxide nanoparticle-assisted laser desorption/ionization mass spectrometry for medical applications

NASA Astrophysics Data System (ADS)

Taira, Shu; Kitajima, Kenji; Katayanagi, Hikaru; Ichiishi, Eiichiro; Ichiyanagi, Yuko

2009-06-01

We prepared and characterized manganese oxide magnetic nanoparticles (d =5.6 nm) and developed nanoparticle-assited laser desorption/ionization (nano-PALDI) mass spectrometry. The nanoparticles had MnO2 and Mn2O3 cores conjugated with hydroxyl and amino groups, and showed paramagnetism at room temperature. The nanoparticles worked as an ionization assisting reagent in mass spectroscopy. The mass spectra showed no background in the low m/z. The nanoparticles could ionize samples of peptide, drug and proteins (approx. 5000 Da) without using matrix, i.e., 2,5-dihydroxybenzoic acid (DHB), 4-hydroxy-α-cinnamic acid (CHCA) and liquid matrix, as conventional ionization assisting reagents. Post source decay spectra by nano-PALDI mass spectrometry will yield information of the chemical structure of analytes.

Laser mass spectrometry of chemical warfare agents using ultrashort laser pulses

NASA Astrophysics Data System (ADS)

Weickhardt, C.; Grun, C.; Grotemeyer, J.

1998-12-01

Fast relaxation processes in excited molecules such as IC, ISC, and fragmentation are observed in many environmentally and technically relevant substances. They cause severe problems to resonance ionization mass spectrometry because they reduce the ionization yield and lead to mass spectra which do not allow the identification of the compound. By the use of ultrashort laser pulses these problems can be overcome and the advantages of REMPI over conventional ionization techniques in mass spectrometry can be regained. This is demonstrated using soil samples contaminated with a chemical warfare agent.

Physical parameters for proton induced K-, L-, and M-shell ionization processes

NASA Astrophysics Data System (ADS)

Shehla; Puri, Sanjiv

2016-10-01

The proton induced atomic inner-shell ionization processes comprising radiative and non-radiative transitions are characterized by physical parameters, namely, the proton ionization cross sections, X-ray emission rates, fluorescence yields and Coster-Kronig (CK) transition probabilities. These parameters are required to calculate the K/L/M shell X-ray production (XRP) cross sections and relative X-ray intensity ratios, which in turn are required for different analytical applications. The current status of different physical parameters is presented in this report for use in various applications.

AMS+ALS: Kinetic and Product Studies of the Heterogeneous Oxidation of Organic Aerosol at the Advanced Light Source

NASA Astrophysics Data System (ADS)

Kroll, J. H.; Wilson, K. R.; Kessler, S. H.; Browne, E. C.; Nah, T.; Smith, J.; Worsnop, D. R.

2014-12-01

The atmospheric oxidation of condensed-phase organic species can have a major influence on the composition, properties, and impacts of organic aerosol (OA); however the rates and products of such "aging" reactions are poorly constrained. Here we describe a series of laboratory experiments aimed at better understanding one class of aging reactions, the heterogeneous oxidation of OA by gas-phase oxidants. Central to these experiments is the availability of vacuum ultraviolet (VUV) light at the Chemical Dynamics Beamline of the Advanced Light Source at LBNL, which enables the implementation of VUV photoionization aerosol mass spectrometry. This technique allows for the real-time, speciated measurement of OA composition, yielding molecular information that is highly complementary to ensemble data from electron-impact ionization. OA composition is measured with both ionization schemes as a function of oxidant exposure within a flow reactor, providing detailed information on the kinetics and products of heterogeneous oxidation over multiple generations of oxidation. Specific topics investigated include the branching between functionalization and fragmentation of OA components, the formation of secondary organic aerosol from photolytically-generated radical species, and the heterogeneous aging of soot-associated organic species.

Quantum state-resolved probing of strong-field-ionized xenon atoms using femtosecond high-order harmonic transient absorption spectroscopy.

PubMed

Loh, Zhi-Heng; Khalil, Munira; Correa, Raoul E; Santra, Robin; Buth, Christian; Leone, Stephen R

2007-04-06

Femtosecond high-order harmonic transient absorption spectroscopy is used to resolve the complete |j,m quantum state distribution of Xe+ produced by optical strong-field ionization of Xe atoms at 800 nm. Probing at the Xe N4/5 edge yields a population distribution rhoj,|m| of rho3/2,1/2ratiorho1/2,1/2ratiorho3/2,3/2=75+/-6 :12+/-3 :13+/-6%. The result is compared to a tunnel ionization calculation with the inclusion of spin-orbit coupling, revealing nonadiabatic ionization behavior. The sub-50-fs time resolution paves the way for tabletop extreme ultraviolet absorption probing of ultrafast dynamics.

Classical vs. evolved quenching parameters and procedures in scintillation measurements: The importance of ionization quenching

NASA Astrophysics Data System (ADS)

Bagán, H.; Tarancón, A.; Rauret, G.; García, J. F.

2008-07-01

The quenching parameters used to model detection efficiency variations in scintillation measurements have not evolved since the decade of 1970s. Meanwhile, computer capabilities have increased enormously and ionization quenching has appeared in practical measurements using plastic scintillation. This study compares the results obtained in activity quantification by plastic scintillation of 14C samples that contain colour and ionization quenchers, using classical (SIS, SCR-limited, SCR-non-limited, SIS(ext), SQP(E)) and evolved (MWA-SCR and WDW) parameters and following three calibration approaches: single step, which does not take into account the quenching mechanism; two steps, which takes into account the quenching phenomena; and multivariate calibration. Two-step calibration (ionization followed by colour) yielded the lowest relative errors, which means that each quenching phenomenon must be specifically modelled. In addition, the sample activity was quantified more accurately when the evolved parameters were used. Multivariate calibration-PLS also yielded better results than those obtained using classical parameters, which confirms that the quenching phenomena must be taken into account. The detection limits for each calibration method and each parameter were close to those obtained theoretically using the Currie approach.

Study of genetic effects of high energy radiations with different ionizing capacities on extracellular phages.

PubMed

Bresler, S E; Kalinin, V L; Kopylova, Y U; Krivisky, A S; Rybchin, V N; Shelegedin, V N

1975-07-01

The inactivating and mutagenic action of high-energy radiations with different ionizing capacities (gamma-rays, protons, alpha-particles and accelerated ions of 12C and 20Ne) was studied by using coliphages lambda11 and SD as subjects. In particular the role of irradiation conditions (broth suspension, pure buffer, dry samples) and of the host functions recA, exrA and polA was investigated. The dose-response curve of induced mutagenesis was studied by measuring the yield of vir mutants in lambda11 and plaque mutants in SD. The following results were obtained. (1) The inactivation kinetics of phages under the action of gamma-rays and protons was first order to a survival of 10(-7). Heavy ions also showed exponential inactivation kinetics to a survival of 10(-4). At higher doses of 20Ne ion bombardment some deviation from one-hit kinetics was observed. For dry samples of phages the dimensions of targets for all types of radiation were approximately proportional to the molecular weights of phage DNA's. For densely ionizing radiation (heavy ions) the inactivating action was 3-5 times weaker than for gamma-rays and protons. (2) Mutagenesis was observed for all types of radiation, but heavy ions were 1-5-2 times less efficient than gamma-rays. For both phages studied the dose-response curve of mutagenesis was non-linear. The dependence on the dose was near to parabolic for lambda11. For SD a plateau or maximum of mutagenesis was observed for the relative number of mutants at a survival of about 10(-4). (3) Host-cell functions recA and exrA were practically indifferent for survival of gamma-irradiated phage lambda11, but indispensable for mutagenesis. Mutation recAI3 abolished induced vir mutations totally and exrA- reduced them significantly. The absence of the function polA had a considerable influence on phage survival, but no effect on vir mutation yield (if compared at the same survival level). (4) In conditions of indirect action of gamma-rays no vir mutations were induced. This is regarded as evidence that the single-strand breaks formed under indirect action conditions cannot serve as pre-mutational damage in DNA.

Determination of structure parameters in strong-field tunneling ionization theory of molecules

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

Zhao Songfeng; Jin Cheng; College of Physics and Electronic Engineering, Northwest Normal University, Lanzhou, Gansu 730070

2010-03-15

In the strong field molecular tunneling ionization theory of Tong et al. [Phys. Rev. A 66, 033402 (2002)], the ionization rate depends on the asymptotic wave function of the molecular orbital from which the electron is removed. The orbital wave functions obtained from standard quantum chemistry packages in general are not good enough in the asymptotic region. Here we construct a one-electron model potential for several linear molecules using density functional theory. We show that the asymptotic wave function can be improved with an iteration method and after one iteration accurate asymptotic wave functions and structure parameters are determined. Withmore » the new parameters we examine the alignment-dependent tunneling ionization probabilities for several molecules and compare with other calculations and with recent measurements, including ionization from inner molecular orbitals.« less

MCDF calculations of Auger cascade processes

NASA Astrophysics Data System (ADS)

Beerwerth, Randolf; Fritzsche, Stephan

2017-10-01

We model the multiple ionization of near-neutral core-excited atoms where a cascade of Auger processes leads to the emission of several electrons. We utilize the multiconfiguration Dirac-Fock (MCDF) method to generate approximate wave functions for all fine-structure levels and to account for all decays between them. This approach allows to compute electron spectra, the population of final-states and ion yields, that are accessible in many experiments. Furthermore, our approach is based on the configuration interaction method. A careful treatment of correlation between electronic configurations enables one to model three-electron processes such as an Auger decay that is accompanied by an additional shake-up transition. Here, this model is applied to the triple ionization of atomic cadmium, where we show that the decay of inner-shell 4p holes to triply-charged final states is purely due to the shake-up transition of valence 5s electrons. Contribution to the Topical Issue "Atomic and Molecular Data and their Applications", edited by Gordon W.F. Drake, Jung-Sik Yoon, Daiji Kato, Grzegorz Karwasz.

Unusual Complex Formation and Chemical Reaction of Haloacetate Anion on the Exterior Surface of Cucurbit[6]uril in the Gas Phase

NASA Astrophysics Data System (ADS)

Choi, Tae Su; Ko, Jae Yoon; Heo, Sung Woo; Ko, Young Ho; Kim, Kimoon; Kim, Hugh I.

2012-10-01

Noncovalent interactions of cucurbit[6]uril (CB[6]) with haloacetate and halide anions are investigated in the gas phase using electrospray ionization ion mobility mass spectrometry. Strong noncovalent interactions of monoiodoacetate, monobromoacetate, monochloroacetate, dichloroacetate, and trichloroacetate on the exterior surface of CB[6] are observed in the negative mode electrospray ionization mass spectra. The strong binding energy of the complex allows intramolecular SN2 reaction of haloacetate, which yields externally bound CB[6]-halide complex, by collisional activation. Utilizing ion mobility technique, structures of exteriorly bound CB[6] complexes of haloacetate and halide anions are confirmed. Theoretically determined low energy structures using density functional theory (DFT) further support results from ion mobility studies. The DFT calculation reveals that the binding energy and conformation of haloacetate on the CB[6] surface affect the efficiency of the intramolecular SN2 reaction of haloacetate, which correlate well with the experimental observation.

Kinematically complete study of low-energy electron-impact ionization of argon: Internormalized cross sections in three-dimensional kinematics

NASA Astrophysics Data System (ADS)

Ren, Xueguang; Amami, Sadek; Zatsarinny, Oleg; Pflüger, Thomas; Weyland, Marvin; Dorn, Alexander; Madison, Don; Bartschat, Klaus

2016-06-01

As a further test of advanced theoretical methods to describe electron-impact single-ionization processes in complex atomic targets, we extended our recent work on Ne (2 p ) ionization [X. Ren, S. Amami, O. Zatsarinny, T. Pflüger, M. Weyland, W. Y. Baek, H. Rabus, K. Bartschat, D. Madison, and A. Dorn, Phys. Rev. A 91, 032707 (2015), 10.1103/PhysRevA.91.032707] to Ar (3 p ) ionization at the relatively low incident energy of E0=66 eV. The experimental data were obtained with a reaction microscope, which can cover nearly the entire 4 π solid angle for the secondary electron emission. We present experimental data for detection angles of 10, 15, and 20∘ for the faster of the two outgoing electrons as a function of the detection angle of the secondary electron with energies of 3, 5, and 10 eV, respectively. Comparison with theoretical predictions from a B -spline R -matrix (BSR) with pseudostates approach and a three-body distorted-wave (3DW) approach, for detection of the secondary electron in three orthogonal planes as well as the entire solid angle, shows overall satisfactory agreement between experiment and the BSR results, whereas the 3DW approach faces difficulties in predicting some of the details of the angular distributions. These findings are different from our earlier work on Ne (2 p ), where both the BSR and 3DW approaches yielded comparable levels of agreement with the experimental data.

Electron-Transfer Secondary Reaction Matrices for MALDI MS Analysis of Bacteriochlorophyll a in Rhodobacter sphaeroides and Its Zinc and Copper Analogue Pigments

NASA Astrophysics Data System (ADS)

Calvano, Cosima Damiana; Ventura, Giovanni; Trotta, Massimo; Bianco, Giuliana; Cataldi, Tommaso R. I.; Palmisano, Francesco

2017-01-01

Bacteriochlorophyll a ( BChl a), a photosynthetic pigment performing the same functions of chlorophylls in plants, features a bacteriochlorin macrocycle ring (18 π electrons) with two reduced pyrrole rings along with a hydrophobic terpenoid side chain (i.e., the phytol residue). Chlorophylls analysis by matrix-assisted laser desorption/ionization mass spectrometry (MALDI MS) is not so straightforward since pheophytinization (i.e., release of the central metal ion) and cleavage of the phytol-ester linkage are invariably observed by employing protonating matrices such as 2,5-dihydroxybenzoic acid, sinapinic acid, and α-cyano-4-hydroxycinnamic acid. Using BChl a from Rhodobacter sphaeroides R26 strain as a model system, different electron-transfer (ET) secondary reaction matrices, leading to the formation of almost stable radical ions in both positive ([M]+•) and negative ([M]-•) ionization modes at m/z 910.55, were evaluated. Compared with ET matrices such as trans-2-[3-(4-t-butyl-phenyl)-2-methyl-2-propenylidene]malononitrile (DCTB), 2,2':5',2''-terthiophene (TER), anthracene (ANT), and 9,10-diphenylanthracene (DP-ANT), 1,5-diaminonaphthalene (DAN) was found to provide the highest ionization yield with a negligible fragmentation. DAN also displayed excellent ionization properties for two metal ion-substituted bacteriochlorophylls, (i.e., Zn- and Cu-BChl a at m/z 950.49 and 949.49), respectively. MALDI MS/MS of both radical charged molecular species provide complementary information, thus making analyte identification more straightforward.

Time-Dependent Photoionization of Gaseous Nebulae: The Pure Hydrogen Case

NASA Technical Reports Server (NTRS)

Garcia, J.; Elhoussieny, E. E.; Bautista, M. A.; Kallman, Timothy R.

2013-01-01

We study the problem of time-dependent photoionization of low density gaseous nebulae subjected to sudden changes in the intensity of ionizing radiation. To this end, we write a computer code that solves the full timedependent energy balance, ionization balance, and radiation transfer equations in a self-consistent fashion for a simplified pure hydrogen case. It is shown that changes in the ionizing radiation yield ionizationthermal fronts that propagate through the cloud, but the propagation times and response times to such fronts vary widely and nonlinearly from the illuminated face of the cloud to the ionization front (IF). IFthermal fronts are often supersonic, and in slabs initially in pressure equilibrium such fronts yield large pressure imbalances that are likely to produce important dynamical effects in the cloud. Further, we studied the case of periodic variations in the ionizing flux. It is found that the physical conditions of the plasma have complex behaviors that differ from any steady-state solution. Moreover, even the time average of ionization and temperature is different from any steady-state case. This time average is characterized by overionization and a broader IF with respect to the steady-state solution for a mean value of the radiation flux. Around the time average of physical conditions there is a large dispersion in instantaneous conditions, particularly across the IF, which increases with the period of radiation flux variations. Moreover, the variations in physical conditions are asynchronous along the slab due to the combination of nonlinear propagation times for thermal frontsIFs and equilibration times.

Energy Balance for a Sonoluminescence Bubble Yields a Measure of Ionization Potential Lowering

NASA Astrophysics Data System (ADS)

Kappus, B.; Bataller, A.; Putterman, S. J.

2013-12-01

Application of energy conservation between input sound and the microplasma which forms at the moment of sonoluminescence places bounds on the process, whereby the gas is ionized. Detailed pulsed Mie scattering measurements of the radius versus time for a xenon bubble in sulfuric acid provide a complete characterization of the hydrodynamics and minimum radius. For a range of emission intensities, the blackbody spectrum emitted during collapse matches the minimum bubble radius, implying opaque conditions are attained. This requires a degree of ionization >36%. Analysis reveals only 2.1±0.6eV/atom of energy available during light emission. In order to unbind enough charge, collective processes must therefore reduce the ionization potential by at least 75%. We interpret this as evidence that a phase transition to a highly ionized plasma is occurring during sonoluminescence.

Energy balance for a sonoluminescence bubble yields a measure of ionization potential lowering.

PubMed

Kappus, B; Bataller, A; Putterman, S J

2013-12-06

Application of energy conservation between input sound and the microplasma which forms at the moment of sonoluminescence places bounds on the process, whereby the gas is ionized. Detailed pulsed Mie scattering measurements of the radius versus time for a xenon bubble in sulfuric acid provide a complete characterization of the hydrodynamics and minimum radius. For a range of emission intensities, the blackbody spectrum emitted during collapse matches the minimum bubble radius, implying opaque conditions are attained. This requires a degree of ionization >36%. Analysis reveals only 2.1±0.6  eV/atom of energy available during light emission. In order to unbind enough charge, collective processes must therefore reduce the ionization potential by at least 75%. We interpret this as evidence that a phase transition to a highly ionized plasma is occurring during sonoluminescence.

Epoch of reionization 21 cm forecasting from MCMC-constrained semi-numerical models

NASA Astrophysics Data System (ADS)

Hassan, Sultan; Davé, Romeel; Finlator, Kristian; Santos, Mario G.

2017-06-01

The recent low value of Planck Collaboration XLVII integrated optical depth to Thomson scattering suggests that the reionization occurred fairly suddenly, disfavouring extended reionization scenarios. This will have a significant impact on the 21 cm power spectrum. Using a semi-numerical framework, we improve our model from instantaneous to include time-integrated ionization and recombination effects, and find that this leads to more sudden reionization. It also yields larger H II bubbles that lead to an order of magnitude more 21 cm power on large scales, while suppressing the small-scale ionization power. Local fluctuations in the neutral hydrogen density play the dominant role in boosting the 21 cm power spectrum on large scales, while recombinations are subdominant. We use a Monte Carlo Markov chain approach to constrain our model to observations of the star formation rate functions at z = 6, 7, 8 from Bouwens et al., the Planck Collaboration XLVII optical depth measurements and the Becker & Bolton ionizing emissivity data at z ˜ 5. We then use this constrained model to perform 21 cm forecasting for Low Frequency Array, Hydrogen Epoch of Reionization Array and Square Kilometre Array in order to determine how well such data can characterize the sources driving reionization. We find that the Mock 21 cm power spectrum alone can somewhat constrain the halo mass dependence of ionizing sources, the photon escape fraction and ionizing amplitude, but combining the Mock 21 cm data with other current observations enables us to separately constrain all these parameters. Our framework illustrates how the future 21 cm data can play a key role in understanding the sources and topology of reionization as observations improve.

Technical report. The application of probability-generating functions to linear-quadratic radiation survival curves.

PubMed

Kendal, W S

2000-04-01

To illustrate how probability-generating functions (PGFs) can be employed to derive a simple probabilistic model for clonogenic survival after exposure to ionizing irradiation. Both repairable and irreparable radiation damage to DNA were assumed to occur by independent (Poisson) processes, at intensities proportional to the irradiation dose. Also, repairable damage was assumed to be either repaired or further (lethally) injured according to a third (Bernoulli) process, with the probability of lethal conversion being directly proportional to dose. Using the algebra of PGFs, these three processes were combined to yield a composite PGF that described the distribution of lethal DNA lesions in irradiated cells. The composite PGF characterized a Poisson distribution with mean, chiD+betaD2, where D was dose and alpha and beta were radiobiological constants. This distribution yielded the conventional linear-quadratic survival equation. To test the composite model, the derived distribution was used to predict the frequencies of multiple chromosomal aberrations in irradiated human lymphocytes. The predictions agreed well with observation. This probabilistic model was consistent with single-hit mechanisms, but it was not consistent with binary misrepair mechanisms. A stochastic model for radiation survival has been constructed from elementary PGFs that exactly yields the linear-quadratic relationship. This approach can be used to investigate other simple probabilistic survival models.

Matrix effects on secondary ion emission from a room-temperature ionic liquid, 1-ethyl-3-methylimidazolium bis[trifluoromethanesulfonyl]imide

NASA Astrophysics Data System (ADS)

Souda, Ryutaro

2009-06-01

The ionization mechanism of room-temperature ionic liquids has been investigated using time-of-flight secondary ion mass spectrometry in the temperature range of 15-300 K. Analyses of 1-ethyl-3-methylimidazolium bis[trifluoromethanesulfonyl]imide ([emim][Tf2N]) deposited on a Ni(111) substrate revealed that the [emim]+ and [Tf2N]- yields increase together with the Ni+ yield at monolayer coverage; no such increase was observed for the films deposited on a D2O spacer layer. Results indicated that the [emim][Tf2N] molecule is not perfectly ionized; the Ni(111) surface accepts (for [emim]+) or donates (for [Tf2N]-) an electron with higher efficiency than the counterion because of the metal band effect. This phenomenon might be induced by electrostatic interactions between the separated cation and anion during sputtering. It is also suggested that the sputtered Ni atom can be ionized nonadiabatically by the formation of a quasimolecule with adspecies. The multilayer of [emim][Tf2N] deposited at 15 K has a porous structure, resembling that of polar molecules, because of nonionic intermolecular interactions. The phase transition is identifiable, together with the morphological change in the crystalline film, from temperature evolutions of the secondary ion yields.

Dynamics of the CRRES barium releases in the magnetosphere

NASA Technical Reports Server (NTRS)

Fuselier, S. A.; Mende, S. B.; Geller, S. P.; Miller, M.; Hoffman, R. A.; Wygant, J. R.; Pongratz, M.; Meredith, N. P.; Anderson, R. R.

1994-01-01

The Combined Release and Radiation Effects Satellite (CRRES) G-2, G-3, and G-4 ionized and neutral barium cloud positions are triangulated from ground-based optical data. From the time history of the ionized cloud motion perpendicular to the magnetic field, the late time coupling of the ionized cloud with the collisionless ambient plasma in the magnetosphere is investigated for each of the releases. The coupling of the ionized clouds with the ambient medium is quantitatively consistent with predictions from theory in that the coupling time increases with increasing distance from the Earth. Quantitative comparison with simple theory for the couping time also yields reasonable agreement. Other effects not predicted by the theory are discussed in the context of the observations.

Giant plasmon excitation in single and double ionization of C60 by fast highly charged Si and O ions

NASA Astrophysics Data System (ADS)

Kelkar, A. H.; Kadhane, U.; Misra, D.; Tribedi, L. C.

2007-09-01

Se have investigated single and double ionization of C60 molecule in collisions with 2.33 MeV/u Siq+ (q=6-14) and 3.125 MeV/u Oq+ (q=5-8) projectiles. The projectile charge state dependence of the single and double ionization yields of C60 are then compared to those for an ion-atom collision system using Ne gas as a target. A large difference between the gas and the cluster target behaviour was partially explained in terms of a model based on collective excitation namely the giant dipole plasmon resonance (GDPR). The qualitative agreement between the data and GDPR model prediction for single and double ionization signifies the importance of single and double plasmon excitations in the ionization process. A large deviation of the GDPR model for triple and quadruple ionization from the experimental data imply the importance of the other low impact parameter processes such as evaporation, fragmentation and a possible solid-like dynamical screening.

Carbon Nanotube Fiber Ionization Mass Spectrometry: A Fundamental Study of a Multi-Walled Carbon Nanotube Functionalized Corona Discharge Pin for Polycyclic Aromatic Hydrocarbons Analysis.

PubMed

Nahan, Keaton S; Alvarez, Noe; Shanov, Vesselin; Vonderheide, Anne

2017-11-01

Mass spectrometry continues to tackle many complicated tasks, and ongoing research seeks to simplify its instrumentation as well as sampling. The desorption electrospray ionization (DESI) source was the first ambient ionization source to function without extensive gas requirements and chromatography. Electrospray techniques generally have low efficiency for ionization of nonpolar analytes and some researchers have resorted to methods such as direct analysis in real time (DART) or desorption atmospheric pressure chemical ionization (DAPCI) for their analysis. In this work, a carbon nanotube fiber ionization (nanoCFI) source was developed and was found to be capable of solid phase microextraction (SPME) of nonpolar analytes as well as ionization and sampling similar to that of direct probe atmospheric pressure chemical ionization (DP-APCI). Conductivity and adsorption were maintained by utilizing a corona pin functionalized with a multi-walled carbon nanotube (MWCNT) thread. Quantitative work with the nanoCFI source with a designed corona discharge pin insert demonstrated linearity up to 0.97 (R 2 ) of three target PAHs with phenanthrene internal standard. Graphical Abstract ᅟ.

Carbon Nanotube Fiber Ionization Mass Spectrometry: A Fundamental Study of a Multi-Walled Carbon Nanotube Functionalized Corona Discharge Pin for Polycyclic Aromatic Hydrocarbons Analysis

NASA Astrophysics Data System (ADS)

Nahan, Keaton S.; Alvarez, Noe; Shanov, Vesselin; Vonderheide, Anne

2017-09-01

Mass spectrometry continues to tackle many complicated tasks, and ongoing research seeks to simplify its instrumentation as well as sampling. The desorption electrospray ionization (DESI) source was the first ambient ionization source to function without extensive gas requirements and chromatography. Electrospray techniques generally have low efficiency for ionization of nonpolar analytes and some researchers have resorted to methods such as direct analysis in real time (DART) or desorption atmospheric pressure chemical ionization (DAPCI) for their analysis. In this work, a carbon nanotube fiber ionization (nanoCFI) source was developed and was found to be capable of solid phase microextraction (SPME) of nonpolar analytes as well as ionization and sampling similar to that of direct probe atmospheric pressure chemical ionization (DP-APCI). Conductivity and adsorption were maintained by utilizing a corona pin functionalized with a multi-walled carbon nanotube (MWCNT) thread. Quantitative work with the nanoCFI source with a designed corona discharge pin insert demonstrated linearity up to 0.97 (R2) of three target PAHs with phenanthrene internal standard. [Figure not available: see fulltext.

Laser-Induced Ionization Efficiency Enhancement On A Filament For Thermal Ionization Mass Spectrometry

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

Siegfried, M.

2015-10-14

The evaluation of trace Uranium and Plutonium isotope ratios for nanogram to femtogram material quantities is a vital tool for nuclear counter-proliferation and safeguard activities. Thermal Ionization Mass Spectrometry (TIMS) is generally accepted as the state of the art technology for highly accurate and ultra-trace measurements of these actinide ratios. However, the very low TIMS ionization yield (typically less than 1%) leaves much room for improvement. Enhanced ionization of Nd and Sm from a TIMS filament was demonstrated using wavelength resonance with a nanosecond (pulse width) laser operating at 10 Hz when light was directed toward the filament.1 For thismore » study, femtosecond and picosecond laser capabilities were to be employed to study the dissociation and ionization mechanisms of actinides/lanthanides and measure the enhanced ionization of the metal of interest. Since the underlying chemistry of the actinide/lanthanide carbides produced and dissociated on a TIMS filament is not well understood, the experimental parameters affecting the photodissociation and photoionization with one and two laser beams were to be investigated.« less

Dynamic Reactive Ionization with Cluster Secondary Ion Mass Spectrometry

NASA Astrophysics Data System (ADS)

Tian, Hua; Wucher, Andreas; Winograd, Nicholas

2016-02-01

Gas cluster ion beams (GCIB) have been tuned to enhance secondary ion yields by doping small gas molecules such as CH4, CO2, and O2 into an Ar cluster projectile, Arn + ( n = 1000-10,000) to form a mixed cluster. The `tailored beam' has the potential to expand the application of secondary ion mass spectrometry for two- and three-dimensional molecular specific imaging. Here, we examine the possibility of further enhancing the ionization by doping HCl into the Ar cluster. Water deposited on the target surface facilitates the dissociation of HCl. This concerted effect, occurring only at the impact site of the cluster, arises since the HCl is chemically induced to ionize to H+ and Cl- , allowing improved protonation of neutral molecular species. This hypothesis is confirmed by depth profiling through a trehalose thin film exposed to D2O vapor, resulting in ~20-fold increase in protonated molecules. The results show that it is possible to dynamically maintain optimum ionization conditions during depth profiling by proper adjustment of the water vapor pressure. H-D exchange in the trehalose molecule M was monitored upon deposition of D2O on the target surface, leading to the observation of [Mn* + H]+ or [Mn* + D]+ ions, where n = 1-8 hydrogen atoms in the trehalose molecule M have been replaced by deuterium. In general, we discuss the role of surface chemistry and dynamic reactive ionization of organic molecules in increasing the secondary ion yield.

Influence of spokes on the ionized metal flux fraction in chromium high power impulse magnetron sputtering

NASA Astrophysics Data System (ADS)

Biskup, B.; Maszl, C.; Breilmann, W.; Held, J.; Böke, M.; Benedikt, J.; von Keudell, A.

2018-03-01

High power impulse magnetron sputtering (HiPIMS) discharges are an excellent tool for deposition of thin films with superior properties. By adjusting the plasma parameters, an energetic metal and reactive species growth flux can be controlled. This control requires, however, a quantitative knowledge of the ion-to-neutral ratio in the growth flux and of the ion energy distribution function to optimize the deposited energy per incorporated atom in the film. This quantification is performed by combining two diagnostics, a quartz crystal microbalance (QCM) combined with an ion-repelling grid system (IReGS) to discriminate ions versus neutrals and a HIDEN EQP plasma monitor to measure the ion energy distribution function (IEDF). This approach yields the ionized metal flux fraction (IMFF) as the ionization degree in the growth flux. This is correlated to the plasma performance recorded by time resolved ICCD camera measurements, which allow to identify the formation of pronounced ionization zones, so called spokes, in the HiPIMS plasma. Thereby an automatic technique was developed to identify the spoke mode number. The data indicates two distinct regimes with respect to spoke formation that occur with increasing peak power, a stochastic regime with no spokes at low peak powers followed by a regime with distinct spokes at varying mode numbers at higher peak powers. The IMFF increases with increasing peak power reaching values of almost 80% at very high peak powers. The transition in between the two regimes coincides with a pronounced change in the IMFF. This change indicates that the formation of spokes apparently counteracts the return effect in HiPIMS. Based on the IMFF and the mean energy of the ions, the energy per deposited atom together with the overall energy flux onto the substrate is calculated. This allows us to determine an optimum for the peak power density around 0.5 kW cm-2 for chromium HiPIMS.

Supercritical Carbon Dioxide and Microwave-Assisted Extraction of Functional Lipophilic Compounds from Arthrospira platensis

PubMed Central

Esquivel-Hernández, Diego A.; López, Víctor H.; Rodríguez-Rodríguez, José; Alemán-Nava, Gibrán S.; Cuéllar-Bermúdez, Sara P.; Rostro-Alanis, Magdalena; Parra-Saldívar, Roberto

2016-01-01

Arthrospira platensis biomass was used in order to obtain functional lipophilic compounds through green extraction technologies such as supercritical carbon dioxide fluid extraction (SFE) and microwave-assisted extraction (MAE). The temperature (T) factor was evaluated for MAE, while for SFE, pressure (P), temperature (T), and co-solvent (ethanol) (CS) were evaluated. The maximum extraction yield of the obtained oleoresin was (4.07% ± 0.14%) and (4.27% ± 0.10%) for SFE and MAE, respectively. Extracts were characterized by gas chromatography mass spectrometry (GC-MS) and gas chromatography flame ionization detector (GC-FID). The maximum contents of functional lipophilic compounds in the SFE and MAE extracts were: for carotenoids 283 ± 0.10 μg/g and 629 ± 0.13 μg/g, respectively; for tocopherols 5.01 ± 0.05 μg/g and 2.46 ± 0.09 μg/g, respectively; and for fatty acids 34.76 ± 0.08 mg/g and 15.88 ± 0.06 mg/g, respectively. In conclusion, the SFE process at P 450 bar, T 60 °C and CS 53.33% of CO2 produced the highest yield of tocopherols, carotenoids and fatty acids. The MAE process at 400 W and 50 °C gives the best extracts in terms of tocopherols and carotenoids. For yield and fatty acids, the MAE process at 400 W and 70 °C produced the highest values. Both SFE and MAE showed to be suitable green extraction technologies for obtaining functional lipophilic compounds from Arthrospira platensis. PMID:27164081

Supercritical Carbon Dioxide and Microwave-Assisted Extraction of Functional Lipophilic Compounds from Arthrospira platensis.

PubMed

Esquivel-Hernández, Diego A; López, Víctor H; Rodríguez-Rodríguez, José; Alemán-Nava, Gibrán S; Cuéllar-Bermúdez, Sara P; Rostro-Alanis, Magdalena; Parra-Saldívar, Roberto

2016-05-05

Arthrospira platensis biomass was used in order to obtain functional lipophilic compounds through green extraction technologies such as supercritical carbon dioxide fluid extraction (SFE) and microwave-assisted extraction (MAE). The temperature (T) factor was evaluated for MAE, while for SFE, pressure (P), temperature (T), and co-solvent (ethanol) (CS) were evaluated. The maximum extraction yield of the obtained oleoresin was (4.07% ± 0.14%) and (4.27% ± 0.10%) for SFE and MAE, respectively. Extracts were characterized by gas chromatography mass spectrometry (GC-MS) and gas chromatography flame ionization detector (GC-FID). The maximum contents of functional lipophilic compounds in the SFE and MAE extracts were: for carotenoids 283 ± 0.10 μg/g and 629 ± 0.13 μg/g, respectively; for tocopherols 5.01 ± 0.05 μg/g and 2.46 ± 0.09 μg/g, respectively; and for fatty acids 34.76 ± 0.08 mg/g and 15.88 ± 0.06 mg/g, respectively. In conclusion, the SFE process at P 450 bar, T 60 °C and CS 53.33% of CO₂ produced the highest yield of tocopherols, carotenoids and fatty acids. The MAE process at 400 W and 50 °C gives the best extracts in terms of tocopherols and carotenoids. For yield and fatty acids, the MAE process at 400 W and 70 °C produced the highest values. Both SFE and MAE showed to be suitable green extraction technologies for obtaining functional lipophilic compounds from Arthrospira platensis.

Scattering of low-energetic atoms and molecules from a boron-doped CVD diamond surface

NASA Astrophysics Data System (ADS)

Allenbach, M.; Neuland, M. B.; Riedo, A.; Wurz, P.

2018-01-01

For the detection of low energetic neutral atoms for the remote sensing of space plasmas, charge state conversion surfaces are used to ionize the neutrals for their subsequent measurement. We investigated a boron-doped Chemical Vapor Deposition (CVD) diamond sample for its suitability to serve as a conversion surface on future space missions, such as NASA's Interstellar Mapping and Acceleration Probe. For H and O atoms incident on conversion surface with energies ranging from 195 to 1000 eV and impact angles from 6° to 15° we measured the angular scattering distributions and the ionization yields. Atomic force microscope and laser ablation ionization mass spectrometry analyses were applied to further characterize the sample. Based on a figure-of-merit, which included the ionization yield and angular scatter distribution, the B-doped CVD surface was compared to other, previously characterized conversion surfaces, including e.g. an undoped CVD diamond with a metallized backside. For particle energies below 390 eV the performance of the B-doped CVD conversion surfaces is comparable to surfaces studied before. For higher energies the figure-of-merit indicates a superior performance. From our studies we conclude that the B-doped CVD diamond sample is well suited for its application on future space missions.

Application of paper spray ionization for explosives analysis.

PubMed

Tsai, Chia-Wei; Tipple, Christopher A; Yost, Richard A

2017-10-15

A desired feature in the analysis of explosives is to decrease the time of the entire analysis procedure, including sampling. A recently utilized ambient ionization technique, paper spray ionization (PSI), provides the possibility of combining sampling and ionization. However, an interesting phenomenon that occurs in generating negatively charged ions pose some challenges in applying PSI to explosives analysis. The goal of this work is to investigate the possible solutions for generating explosives ions in negative mode PSI. The analysis of 2,4,6-trinitrotoluene (TNT), pentaerythritol tetranitrate (PETN), octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX), and 1,3,5-trinitroperhydro-1,3,5-triazine (RDX) was performed. Several solvent systems with different surface tensions and additives were compared to determine their effect on the ionization of explosives. The solvents tested include tert-butanol, isopropanol, methanol, and acetonitrile. The additives tested were carbon tetrachloride and ammonium nitrate. Of the solvents tested, isopropanol yielded the best results. In addition, adding ammonium nitrate to the isopropanol enhanced the analyte signal. Experimentally determined limits of detection (LODs) as low as 0.06 ng for PETN, on paper, were observed with isopropanol and the addition of 0.4 mM ammonium nitrate as the spray solution. In addition, the explosive components of two plastic explosive samples, Composition 4 and Semtex, were successfully analyzed via surface sampling when using the developed method. The analysis of explosives using PSI-MS in negative ion mode was achieved. The addition of ammonium nitrate to isopropanol, in general, enhanced the analyte signal and yielded better ionization stability. Real-world explosive samples were analyzed, which demonstrates one of the potential applications of PSI-MS analysis. Copyright © 2017 John Wiley & Sons, Ltd.

Wetting of Functionalized Polyethylene Film Having Ionizable Organic Acids and Bases at the Polymer-Water Interface: Relations between Functional Group Polarity, Extent of Ionization, and Contact Angle with Water.

DTIC Science & Technology

1988-03-01

functional grouos in the interface contribute independently to the interfacial free energy is inaccurate, but leads to a tractable and physically reasonable...nonpolar, non -ionizable groups. As a limiting case, we consider a system *. containing only one type of polar and one type of nonpolar group (eq 9) with A...groups (protonition or deprotonation): these equations apply to both non - ionizable groups and to PE-CO 2H and PE-NR 2H + . Assuming that Figure 3

Fragmentation of a valine molecule by electron impact

NASA Astrophysics Data System (ADS)

Vukstich, V. S.; Romanova, L. G.; Megela, I. G.; Papp, A. V.; Snegurskii, A. V.

2017-05-01

The formation of ion products of single and dissociative ionization of a valine molecule (C5H11NO2) by high-energy (11.5 MeV) and low-energy (below 150 eV) electrons has been investigated by mass spectrometry. Mass spectra of this molecule and near-threshold functions of yield of its ion fragments, for which the magnitudes of occurrence energies are determined, have been obtained. The analysis of the changes in mass spectra of valine molecules irradiated with doses of 5 and 20 kGy in comparison with those for unirradiated molecules shows that high-energy irradiation changes irreversibly the structure of some of the initial molecules.

Structural characterization of saturated branched chain fatty acid methyl esters by collisional dissociation of molecular ions generated by electron ionization[S

PubMed Central

Ran-Ressler, Rinat R.; Lawrence, Peter; Brenna, J. Thomas

2012-01-01

Saturated branched chain fatty acids (BCFA) are present as complex mixtures in numerous biological samples. The traditional method for structure elucidation, electron ionization (EI) mass spectrometry, sometimes does not unambiguously enable assignment of branching in isomeric BCFA. Zirrolli and Murphy (Zirrolli , J. A. , and R. A. Murphy. 1993. Low-energy tandem mass spectrometry of the molecular ion derived from fatty acid methyl esters: a novel method for analysis of branched-chain fatty acids. J. Am. Soc. Mass Spectrom. 4: 223–229.) showed that the molecular ions of four BCFA methyl ester (BCFAME) yield highly characteristic fragments upon collisional dissociation using a triple quadrupole instrument. Here, we confirm and extend these results by analysis using a tabletop 3-D ion trap for activated molecular ion EI-MS/MS to 30 BCFAME. iso-BCFAME produces a prominent ion (30-100% of base peak) for [M-43] (M-C3H7), corresponding to the terminal isopropyl moiety in the original iso-BCFAME. Anteiso-FAME yield prominent ions (20-100% of base peak) corresponding to losses on both side of the methyl branch, [M-29] and [M-57], and tend to produce more prominent m/z 115 peaks corresponding to a cyclization product around the ester. Dimethyl and tetramethyl FAME, with branches separated by at least one methylene group, yield fragment on both sides of the sites of methyl branches that are more than 6 C away from the carboxyl carbon. EI-MS/MS yields uniquely specific ions that enable highly confident structural identification and quantification of BCFAME. PMID:22021637

MALDI-MS/MS with Traveling Wave Ion Mobility for the Structural Analysis of N-Linked Glycans

NASA Astrophysics Data System (ADS)

Harvey, David J.; Scarff, Charlotte A.; Crispin, Max; Scanlan, Christopher N.; Bonomelli, Camille; Scrivens, James H.

2012-11-01

The preference for singly charged ion formation by MALDI makes it a better choice than electrospray ionization for profiling mixtures of N-glycans. For structural analysis, fragmentation of negative ions often yields more informative spectra than fragmentation of positive ones but such ions are more difficult to produce from neutral glycans under MALDI conditions. This work investigates conditions for the formation of both positive and negative ions by MALDI from N-linked glycans released from glycoproteins and their subsequent MS/MS and ion mobility behaviour. 2,4,6-Trihydroxyacetophenone (THAP) doped with ammonium nitrate was found to give optimal ion yields in negative ion mode. Ammonium chloride or phosphate also yielded prominent adducts but anionic carbohydrates such as sulfated N-glycans tended to ionize preferentially. Carbohydrates adducted with all three adducts (phosphate, chloride, and nitrate) produced good negative ion CID spectra but those adducted with iodide and sulfate did not yield fragment ions although they gave stronger signals. Fragmentation paralleled that seen following electrospray ionization providing superior spectra than could be obtained by PSD on MALDI-TOF instruments or with ion traps. In addition, ion mobility drift times of the adducted glycans and the ability of this technique to separate isomers also mirrored those obtained following ESI sample introduction. Ion mobility also allowed profiles to be obtained from samples whose MALDI spectra showed no evidence of such ions allowing the technique to be used in conditions where sample amounts were limiting. The method was applied to N-glycans released from the recombinant human immunodeficiency virus glycoprotein, gp120.

Discovery of Novel Saponins from the Viscera of the Sea Cucumber Holothuria lessoni

PubMed Central

Bahrami, Yadollah; Zhang, Wei; Franco, Chris

2014-01-01

Sea cucumbers, sometimes referred to as marine ginseng, produce numerous compounds with diverse functions and are potential sources of active ingredients for agricultural, nutraceutical, pharmaceutical and cosmeceutical products. We examined the viscera of an Australian sea cucumber Holothuria lessoni Massin et al. 2009, for novel bioactive compounds, with an emphasis on the triterpene glycosides, saponins. The viscera were extracted with 70% ethanol, and this extract was purified by a liquid-liquid partition process and column chromatography, followed by isobutanol extraction. The isobutanol saponin-enriched mixture was further purified by high performance centrifugal partition chromatography (HPCPC) with high purity and recovery. The resultant purified polar samples were analyzed using matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS)/MS and electrospray ionization mass spectrometry (ESI-MS)/MS to identify saponins and characterize their molecular structures. As a result, at least 39 new saponins were identified in the viscera of H. lessoni with a high structural diversity, and another 36 reported triterpene glycosides, containing different aglycones and sugar moieties. Viscera samples have provided a higher diversity and yield of compounds than observed from the body wall. The high structural diversity and novelty of saponins from H. lessoni with potential functional activities presents a great opportunity to exploit their applications for industrial, agricultural and pharmaceutical use. PMID:24821624

Efficient ionisation of calcium, strontium and barium by resonant laser pumping

NASA Technical Reports Server (NTRS)

Skinner, C. H.

1980-01-01

Efficient ionization has been observed when an atomic vapor of strontium, barium or calcium was illuminated with a long pulse tunable laser at the frequency of the atomic resonance line. The variation in the degree of ionization with neutral density and laser intensity has been measured using the 'hook' method. The maximum ionization observed was 94%. Excited state populations were measured yielding an excitation temperature (depending on exact experimental conditions) in the region of 0.4 eV. The decay of ion density after the laser pulse was monitored and the recombination coefficients determined. The results are interpreted in terms of an electron heating model.

Critical ionization velocity experiments in space

NASA Astrophysics Data System (ADS)

Lai, Shu T.; Murad, Edmond

1989-07-01

Space experiments to test the critical ionization velocity (CIV) theory have, on the whole, yielded negative results, with two notable exceptions. The results of all the experiments are analyzed with a view towards either optimizing or drawing conclusions about the conditions which lead to the propagation of CIV. In particular, four aspects of the conditions are considered: (1) beam injection angle with the ambient magnetic field in the ionosphere; (2) length of a CIV discharge region in a conical beam; (3) collisional ionization of the neutrals; and (4) chemiionization processes. The analysis leads to the conclusion that using the exhaust of the Shuttle engines may be the best way for testing CIV.

From clusters to bulk: A relativistic density functional investigation on a series of gold clusters Aun, n=6,…,147

NASA Astrophysics Data System (ADS)

Häberlen, Oliver D.; Chung, Sai-Cheong; Stener, Mauro; Rösch, Notker

1997-03-01

A series of gold clusters spanning the size range from Au6 through Au147 (with diameters from 0.7 to 1.7 nm) in icosahedral, octahedral, and cuboctahedral structure has been theoretically investigated by means of a scalar relativistic all-electron density functional method. One of the main objectives of this work was to analyze the convergence of cluster properties toward the corresponding bulk metal values and to compare the results obtained for the local density approximation (LDA) to those for a generalized gradient approximation (GGA) to the exchange-correlation functional. The average gold-gold distance in the clusters increases with their nuclearity and correlates essentially linearly with the average coordination number in the clusters. An extrapolation to the bulk coordination of 12 yields a gold-gold distance of 289 pm in LDA, very close to the experimental bulk value of 288 pm, while the extrapolated GGA gold-gold distance is 297 pm. The cluster cohesive energy varies linearly with the inverse of the calculated cluster radius, indicating that the surface-to-volume ratio is the primary determinant of the convergence of this quantity toward bulk. The extrapolated LDA binding energy per atom, 4.7 eV, overestimates the experimental bulk value of 3.8 eV, while the GGA value, 3.2 eV, underestimates the experiment by almost the same amount. The calculated ionization potentials and electron affinities of the clusters may be related to the metallic droplet model, although deviations due to the electronic shell structure are noticeable. The GGA extrapolation to bulk values yields 4.8 and 4.9 eV for the ionization potential and the electron affinity, respectively, remarkably close to the experimental polycrystalline work function of bulk gold, 5.1 eV. Gold 4f core level binding energies were calculated for sites with bulk coordination and for different surface sites. The core level shifts for the surface sites are all positive and distinguish among the corner, edge, and face-centered sites; sites in the first subsurface layer show still small positive shifts.

Search for Dark Matter Interactions using Ionization Yield in Liquid Xenon

NASA Astrophysics Data System (ADS)

Uvarov, Sergey

Cosmological observations overwhelmingly support the existence of dark matter which constitutes 87% of the universe's total mass. Weakly Interacting Massive Particles (WIMPs) are a prime candidate for dark matter, and the Large Underground Xenon (LUX) experiment aims to a direct-detection of a WIMP-nucleon interaction. The LUX detector is a dual-phase xenon time-projection chamber housed 4,850 feet underground at Sanford Underground Research Facility in Lead, South Dakota. We present the ionization-only analysis of the LUX 2013 WIMP search data. In the 1.04 x 104 kg-days exposure, thirty events were observed out of the 24.8 expected from radioactive backgrounds. We employ a cut-and-count method to set a 1-sided 90% C.L. upper limit for spin-independent WIMP-nucleon cross-sections. A zero charge yield for nuclear-recoils below 0.7 keV is included upper limit calculation. This ionization-only analysis excludes an unexplored region of WIMP-nucleon cross-section for low-mass WIMPs achieving 1.56 x 10-43 cm2 WIMP-nucleon cross-section exclusion for a 5.1 GeV/ c2 WIMP.

Effect of gamma and e-beam radiation on the essential oils of Thymus vulgaris thymoliferum, Eucalyptus radiata, and Lavandula angustifolia.

PubMed

Haddad, Mohamed; Herent, Marie-France; Tilquin, Bernard; Quetin-Leclercq, Joëlle

2007-07-25

The microbiological contamination of raw plant materials is common and may be adequately reduced by radiation processing. This study evaluated the effects of gamma- and e-beam ionizing radiations (25 kGy) on three plants used as food or as medicinal products (Thymus vulgaris L., Eucalyptus radiata D.C., and Lavandula angustifolia Mill.) as well as their effects on extracted or commercial essential oils and pure standard samples. Comparison between irradiated and nonirradiated samples was performed by GC/FID and GC/MS. At the studied doses, gamma and e-beam ionizing radiation did not induce any detectable qualitative or quantitative significant changes in the contents and yields of essential oils immediately after ionizing radiation of plants or commercial essential oils and standards. As the maximum dose tested (25 kGy) is a sterilizing dose (much higher than doses used for decontamination of vegetable drugs), it is likely that even decontamination with lower doses will not modify yields or composition of essential oils of these three plants.

Following electron impact excitation of single (N, O, F, Ne, Na, Mg, Al, Si) atom L subshells ionization cross section calculations by using Lotz's equation

NASA Astrophysics Data System (ADS)

Aydinol, Mahmut

2017-02-01

L shell and L subshells ionization cross sections σL and σLi (i = 1, 2, 3) following electron impact on (N,O, F, Ne, Na, Mg, Al, Si) atoms calculated. By using Lotz' equation for nonrelativistic cases in Matlab σL and σLi cross section values obtained for ten electron impact(Eo) values in the range of ELi

Chemical vapor deposition of aminopropyl silanes in microfluidic channels for highly efficient microchip capillary electrophoresis-electrospray ionization-mass spectrometry.

PubMed

Batz, Nicholas G; Mellors, J Scott; Alarie, Jean Pierre; Ramsey, J Michael

2014-04-01

We describe a chemical vapor deposition (CVD) method for the surface modification of glass microfluidic devices designed to perform electrophoretic separations of cationic species. The microfluidic channel surfaces were modified using aminopropyl silane reagents. Coating homogeneity was inferred by precise measurement of the separation efficiency and electroosmotic mobility for multiple microfluidic devices. Devices coated with (3-aminopropyl)di-isopropylethoxysilane (APDIPES) yielded near diffusion-limited separations and exhibited little change in electroosmotic mobility between pH 2.8 and pH 7.5. We further evaluated the temporal stability of both APDIPES and (3-aminopropyl)triethoxysilane (APTES) coatings when stored for a total of 1 week under vacuum at 4 °C or filled with pH 2.8 background electrolyte at room temperature. Measurements of electroosmotic flow (EOF) and separation efficiency during this time confirmed that both coatings were stable under both conditions. Microfluidic devices with a 23 cm long, serpentine electrophoretic separation channel and integrated nanoelectrospray ionization emitter were CVD coated with APDIPES and used for capillary electrophoresis (CE)-electrospray ionization (ESI)-mass spectrometry (MS) of peptides and proteins. Peptide separations were fast and highly efficient, yielding theoretical plate counts over 600,000 and a peak capacity of 64 in less than 90 s. Intact protein separations using these devices yielded Gaussian peak profiles with separation efficiencies between 100,000 and 400,000 theoretical plates.

Strong-field ionization of Li and Be: a time-dependent density functional theory with self-interaction correction

NASA Astrophysics Data System (ADS)

Telnov, Dmitry A.; Heslar, John T.; Chu, Shih-I.

2011-11-01

In the framework of the time-dependent density functional theory, we have performed 3D calculations of multiphoton ionization of Li and Be atoms by strong near-infrared laser fields. The results for the intensity-dependent probabilities of single and double ionization are presented. We make use of the time-dependent Krieger-Li-Iafrate exchange-correlation potential with self-interaction correction (TD-KLI-SIC). Such a potential possesses an integer discontinuity which improves description of the ionization process. However, we have found that the discontinuity of the TD-KLI-SIC potential is not sufficient to reproduce characteristic feature of double ionization.

Construction of exchange-correlation functionals through interpolation between the non-interacting and the strong-correlation limit

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

Zhou, Yongxi; Ernzerhof, Matthias, E-mail: Matthias.Ernzerhof@UMontreal.ca; Bahmann, Hilke

Drawing on the adiabatic connection of density functional theory, exchange-correlation functionals of Kohn-Sham density functional theory are constructed which interpolate between the extreme limits of the electron-electron interaction strength. The first limit is the non-interacting one, where there is only exchange. The second limit is the strong correlated one, characterized as the minimum of the electron-electron repulsion energy. The exchange-correlation energy in the strong-correlation limit is approximated through a model for the exchange-correlation hole that is referred to as nonlocal-radius model [L. O. Wagner and P. Gori-Giorgi, Phys. Rev. A 90, 052512 (2014)]. Using the non-interacting and strong-correlated extremes, variousmore » interpolation schemes are presented that yield new approximations to the adiabatic connection and thus to the exchange-correlation energy. Some of them rely on empiricism while others do not. Several of the proposed approximations yield the exact exchange-correlation energy for one-electron systems where local and semi-local approximations often fail badly. Other proposed approximations generalize existing global hybrids by using a fraction of the exchange-correlation energy in the strong-correlation limit to replace an equal fraction of the semi-local approximation to the exchange-correlation energy in the strong-correlation limit. The performance of the proposed approximations is evaluated for molecular atomization energies, total atomic energies, and ionization potentials.« less

Density-Functional Theory with Optimized Effective Potential and Self-Interaction Correction for the Double Ionization of He and Be Atoms

NASA Astrophysics Data System (ADS)

Heslar, John; Telnov, Dmitry; Chu, Shih-I.

2012-06-01

We present a self-interaction-free (SIC) time-dependent density-functional theory (TDDFT) for the treatment of double ionization processes of many-electron systems. The method is based on the Krieger-Li-Iafrate (KLI) treatment of the optimized effective potential (OEP) theory and the incorporation of an explicit self-interaction correction (SIC) term. In the framework of the time-dependent density functional theory, we have performed 3D calculations of double ionization of He and Be atoms by strong near-infrared laser fields. We make use of the exchange-correlation potential with the integer discontinuity which improves the description of the double ionization process. We found that proper description of the double ionization requires the TDDFT exchange-correlation potential with the discontinuity with respect to the variation of the spin particle numbers (SPN) only. The results for the intensity-dependent probabilities of single and double ionization are presented and reproduce the famous ``knee'' structure.

Electron affinities and ionization energies of Cu and Ag delafossite compounds: A hybrid functional study

NASA Astrophysics Data System (ADS)

Miao, Mao-Sheng; Yarbro, Sam; Barton, Phillip T.; Seshadri, Ram

2014-01-01

Using density functional theory with a hybrid functional, we calculate the ionization energies and electron affinities of a series of delafossite compounds (AMO2: A =Cu, Ag; M =B, Al, Ga, In, Sc). The alignments of the valence band maximum and the conduction band minimum, which directly relate to the ionization energies and electron affinities, were obtained by calculations of supercell slab models constructed in a nonpolar orientation. Our calculations reveal that the ionization energy decreases with an increasing atomic number of group-III elements, and thus suggest an improved p-type doping propensity for heavier compounds. For keeping both a low ionization energy and a band gap of sufficient size, CuScO2 is superior to the Cu-based group-III delafossites. By analyzing the electronic structures, we demonstrate that the compositional trend of the ionization energies and electron affinities is the result of a combined effect of d-band broadening due to Cu(Ag)-Cu(Ag) coupling and a repositioning of the d-band center.

Picoelectrospray Ionization Mass Spectrometry Using Narrow-bore Chemically Etched Emitters

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

Marginean, Ioan; Tang, Keqi; Smith, Richard D.

2014-01-01

Electrospray ionization mass spectrometry (ESI-MS) at flow rates below ~10 nL/min has been only sporadically explored due to difficulty in reproducibly fabricating emitters that can operate at lower flow rates. Here we demonstrate narrow orifice chemically etched emitters for stable electrospray at flow rates as low as 400 pL/min. Depending on the analyte concentration, we observe two types of MS signal response as a function of flow rate. At low concentrations, an optimum flow rate is observed slightly above 1 nL/min, while the signal decreases monotonically with decreasing flow rates at higher concentrations. In spite of lower MS signal, themore » ion utilization efficiency increases exponentially with decreasing flow rate in all cases. No unimolecular response was observed within this flow rate range during the analysis of an equimolar mixture of peptides, indicating that ionization efficiency is an analyte-dependent characteristic in given experimental conditions. While little to no gain in signal-to-noise was achieved at ultralow flow rates for concentration-limited analyses, experiments consuming the same amount of analyte suggest that mass-limited analyses will benefit strongly from the use of low flow rates and avoiding unnecessary sample dilution. By operating under optimal conditions, consumption of just 500 zmol of sample yielded signal-to-noise ratios ~10 for some peptides. These findings have important implications for the analysis of trace biological samples.« less

Defect chemistry and characterization of Hg(1-x)Cd(x)Te

NASA Technical Reports Server (NTRS)

Vydyanath, H. R.

1981-01-01

Undoped mercury cadmium telluride crystals were subjected to high temperature equilibration at temperatures ranging from 400 C to 655 C in various Hg atmospheres. Hall effect and mobility measurements were carried out on the crystals quenched to room temperature subsequent to the high temperature equilibration. The variation of the hole concentration in the cooled crystals at 77 K as a function of the partial pressure of Hg at the equlibration temperatures, together with a comparison of the hole mobility in the undoped samples with that in the copper and phosphorous doped samples yielded a defect model for the undoped crystals, according to which, the undoped crystals are essentially intrinsic at the equilibration temperatures and the native acceptor defects are doubly ionized. Native donor defects appear to be negligible in concentration, implying that the p to n conversion in these alloys is mainly due to residual foreign donor impurities. The thermodynamic constants for the intrinsic excitation process as well as for the incorporation of the doubly ionized native acceptor defects in the undoped crystals were obtained.

Study of Electron Ionization and Fragmentation of Non-hydrated and Hydrated Tetrahydrofuran Clusters

NASA Astrophysics Data System (ADS)

Neustetter, Michael; Mahmoodi-Darian, Masoomeh; Denifl, Stephan

2017-05-01

Mass spectroscopic investigations on tetrahydrofuran (THF, C4H8O), a common model molecule of the DNA-backbone, have been carried out. We irradiated isolated THF and (hydrated) THF clusters with low energy electrons (electron energy 70 eV) in order to study electron ionization and ionic fragmentation. For elucidation of fragmentation pathways, deuterated TDF (C4D8O) was investigated as well. One major observation is that the cluster environment shows overall a protective behavior on THF. However, also new fragmentation channels open in the cluster. In this context, we were able to solve a discrepancy in the literature about the fragment ion peak at mass 55 u in the electron ionization mass spectrum of THF. We ascribe this ion yield to the fragmentation of ionized THF clusters.

Single and multiple ionization of C60 fullerenes and collective effects in collisions with highly charged C, F, and Si ions with energy 3 MeV/u

NASA Astrophysics Data System (ADS)

Kelkar, A. H.; Kadhane, U.; Misra, D.; Gulyas, L.; Tribedi, L. C.

2010-10-01

We have measured absolute cross sections for single, double, triple, and quadruple ionization of C60 in collisions with 3 MeV/u C, F, and Si projectile ions at various projectile charge states. The experiment was performed using the recoil-ion time-of-flight technique. Projectile charge state dependence of the ionization yields was compared mainly with a model based on the giant dipole plasmon resonance (GDPR). In some cases, the continuum-distorted-wave-eikonal-initial-state (CDW-EIS) model which is normally applied for ion-atom collisions was also used as a reference. An excellent qualitative agreement between the experimental data for single and double ionization and the GDPR model predictions was found for all projectile charge states.

Effects of target heating on experiments using Kα and Kβ diagnostics.

PubMed

Palmeri, P; Boutoux, G; Batani, D; Quinet, P

2015-09-01

We describe the impact of heating and ionization on emission from the target of Kα and Kβ radiation induced by the propagation of hot electrons generated by laser-matter interaction. We consider copper as a test case and, starting from basic principles, we calculate the changes in emission wavelength, ionization cross section, and fluorescence yield as Cu is progressively ionized. We have finally considered the more realistic case when hot electrons have a distribution of energies with average energies of 50 and 500 keV (representative respectively of "shock ignition" and of "fast ignition" experiments) and in which the ions are distributed according to ionization equilibrium. In addition, by confronting our theoretical calculations with existing data, we demonstrate that this study offers a generic theoretical background for temperature diagnostics in laser-plasma interactions.

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

PubMed

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.

Effect of wave function on the proton induced L XRP cross sections for 62Sm and 74W

NASA Astrophysics Data System (ADS)

Shehla, Kaur, Rajnish; Kumar, Anil; Puri, Sanjiv

2015-08-01

The Lk(k= 1, α, β, γ) X-ray production cross sections have been calculated for 74W and 62Sm at different incident proton energies ranging 1-5 MeV using theoretical data sets of different physical parameters, namely, the Li(i=1-3) sub-shell X-ray emission rates based on the Dirac-Fork (DF) model, the fluorescence and Coster Kronig yields based on the Dirac- Hartree-Slater (DHS) model and two sets the proton ionization cross sections based on the DHS model and the ECPSSR in order to assess the influence of the wave function on the XRP cross sections. The calculated cross sections have been compared with the measured cross sections reported in the recent compilation to check the reliability of the calculated values.

The accuracy of seminumerical reionization models in comparison with radiative transfer simulations

NASA Astrophysics Data System (ADS)

Hutter, Anne

2018-06-01

We have developed a modular seminumerical code that computes the time and spatially dependent ionization of neutral hydrogen (H I), neutral (He I), and single-ionized helium (He II) in the intergalactic medium (IGM). The model accounts for recombinations and provides different descriptions for the photoionization rate that are used to calculate the residual H I fraction in ionized regions. We compare different seminumerical reionization schemes to a radiative transfer (RT) simulation. We use the RT simulation as a benchmark, and find that the seminumerical approaches produce similar H II and He II morphologies and power spectra of the H I 21 cm signal throughout reionization. As we do not track partial ionization of He II, the extent of the double-ionized helium (He III) regions is consistently smaller. In contrast to previous comparison projects, the ionizing emissivity in our seminumerical scheme is not adjusted to reproduce the redshift evolution of the RT simulation, but directly derived from the RT simulation spectra. Among schemes that identify the ionized regions by the ratio of the number of ionization and absorption events on different spatial smoothing scales, we find those that mark the entire sphere as ionized when the ionization criterion is fulfilled to result in significantly accelerated reionization compared to the RT simulation. Conversely, those that flag only the central cell as ionized yield very similar but slightly delayed redshift evolution of reionization, with up to 20 per cent ionizing photons lost. Despite the overall agreement with the RT simulation, our results suggest that constraining ionizing emissivity-sensitive parameters from seminumerical galaxy formation-reionization models are subject to photon nonconservation.

The accuracy of semi-numerical reionization models in comparison with radiative transfer simulations

NASA Astrophysics Data System (ADS)

Hutter, Anne

2018-03-01

We have developed a modular semi-numerical code that computes the time and spatially dependent ionization of neutral hydrogen (H I), neutral (He I) and singly ionized helium (He II) in the intergalactic medium (IGM). The model accounts for recombinations and provides different descriptions for the photoionization rate that are used to calculate the residual H I fraction in ionized regions. We compare different semi-numerical reionization schemes to a radiative transfer (RT) simulation. We use the RT simulation as a benchmark, and find that the semi-numerical approaches produce similar H II and He II morphologies and power spectra of the H I 21cm signal throughout reionization. As we do not track partial ionization of He II, the extent of the double ionized helium (He III) regions is consistently smaller. In contrast to previous comparison projects, the ionizing emissivity in our semi-numerical scheme is not adjusted to reproduce the redshift evolution of the RT simulation, but directly derived from the RT simulation spectra. Among schemes that identify the ionized regions by the ratio of the number of ionization and absorption events on different spatial smoothing scales, we find those that mark the entire sphere as ionized when the ionization criterion is fulfilled to result in significantly accelerated reionization compared to the RT simulation. Conversely, those that flag only the central cell as ionized yield very similar but slightly delayed redshift evolution of reionization, with up to 20% ionizing photons lost. Despite the overall agreement with the RT simulation, our results suggests that constraining ionizing emissivity sensitive parameters from semi-numerical galaxy formation-reionization models are subject to photon nonconservation.

Calculation of total electron excitation cross-sections and partial electron ionization cross-sections for the elements. Ph.D. Thesis

NASA Technical Reports Server (NTRS)

Green, T. J.

1973-01-01

Computer programs were used to calculate the total electron excitation cross-section for atoms and the partial ionization cross-section. The approximations to the scattering amplitude used are as follows: (1) Born, Bethe, and Modified Bethe for non-exchange excitation; (2) Ochkur for exchange excitation; and (3) Coulomb-Born of non-exchange ionization. The amplitudes are related to the differential cross-sections which are integrated to give the total excitation (or partial ionization) cross-section for the collision. The atomic wave functions used are Hartree-Fock-Slater functions for bound states and the coulomb wave function for the continuum. The programs are presented and the results are examined.

Performance and Self-Consistency of the Generalized Dielectric Dependent Hybrid Functional

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

Brawand, Nicholas P.; Govoni, Marco; Vörös, Márton

Here, we analyze the performance of the recently proposed screened exchange constant functional (SX) on the GW100 test set, and we discuss results obtained at different levels of self-consistency. The SX functional is a generalization of dielectric dependent hybrid functionals to finite systems; it is nonempirical and depends on the average screening of the exchange interaction. We compare results for ionization potentials obtained with SX to those of CCSD(T) calculations and experiments, and we find excellent agreement, on par with recent state of the art methods based on many body perturbation theory. Applying SX perturbatively to correct PBE eigenvalues yieldsmore » improved results in most cases, except for ionic molecules, for which wave function self-consistency is instead crucial. Calculations where wave functions and the screened exchange constant (α SX) are determined self-consistently, and those where α SX is fixed to the value determined within PBE, yield results of comparable accuracy. Perturbative G 0W 0 corrections of eigenvalues obtained with self-consistent αSX are small on average, for all molecules in the GW100 test set.« less

Performance and Self-Consistency of the Generalized Dielectric Dependent Hybrid Functional

DOE PAGES

Brawand, Nicholas P.; Govoni, Marco; Vörös, Márton; ...

2017-05-24

Here, we analyze the performance of the recently proposed screened exchange constant functional (SX) on the GW100 test set, and we discuss results obtained at different levels of self-consistency. The SX functional is a generalization of dielectric dependent hybrid functionals to finite systems; it is nonempirical and depends on the average screening of the exchange interaction. We compare results for ionization potentials obtained with SX to those of CCSD(T) calculations and experiments, and we find excellent agreement, on par with recent state of the art methods based on many body perturbation theory. Applying SX perturbatively to correct PBE eigenvalues yieldsmore » improved results in most cases, except for ionic molecules, for which wave function self-consistency is instead crucial. Calculations where wave functions and the screened exchange constant (α SX) are determined self-consistently, and those where α SX is fixed to the value determined within PBE, yield results of comparable accuracy. Perturbative G 0W 0 corrections of eigenvalues obtained with self-consistent αSX are small on average, for all molecules in the GW100 test set.« less

Effects of liver function on ionized hypocalcaemia following rapid blood transfusion.

PubMed

Chung, H S; Cho, S J; Park, C S

2012-01-01

Hypocalcaemia detrimentally affects the cardiovascular system and massive transfusion-related hypocalcaemia is particularly severe in end-stage liver disease patients undergoing liver transplantation (LT). This study, therefore, compared the severity and duration of ionized hypocalcaemia between patients with normal and impaired liver function. Patients (n = 26 per group) were transfused at a rate of 10 ml/kg within 10 min with packed red blood cells (PRBCs) during LT (group LP) or spinal surgery (group SP), or were infused with 0.9% normal saline during spinal surgery (group SN). Serum levels of ionized calcium were assessed before (T(0)), just after (T(1)), and at 20 (T(2)) and 60 min (T(3)) after transfusion. Transfusion with PRBCs caused more severe ionized hypocalcaemia than 0.9% normal saline at T(1). In contrast to the faster (20 min) normalization in group SP, ionized hypocalcaemia in group LP persisted at T(3). Serum ionized calcium levels at T(3) showed correlations with vital signs, blood glucose, serum potassium, base deficit and lactate. Rapid blood transfusion caused more severe and prolonged ionized hypo calcaemia in patients with liver dysfunction than in those with normal liver function.

A complex-polarization-propagator protocol for magneto-chiral axial dichroism and birefringence dispersion.

PubMed

Cukras, Janusz; Kauczor, Joanna; Norman, Patrick; Rizzo, Antonio; Rikken, Geert L J A; Coriani, Sonia

2016-05-21

A computational protocol for magneto-chiral dichroism and magneto-chiral birefringence dispersion is presented within the framework of damped response theory, also known as complex polarization propagator theory, at the level of time-dependent Hartree-Fock and time-dependent density functional theory. Magneto-chiral dichroism and magneto-chiral birefringence spectra in the (resonant) frequency region below the first ionization threshold of R-methyloxirane and l-alanine are presented and compared with the corresponding results obtained for both the electronic circular dichroism and the magnetic circular dichroism. The additional information content yielded by the magneto-chiral phenomena, as well as their potential experimental detectability for the selected species, is discussed.

Study of poly-L-lysine conformations in aqueous methanol solution by using polarized Raman techniques.

PubMed Central

Shepherd, I W

1976-01-01

Raman polarization measurements of the amide I band are reported in ionized poly-L-lysine dissolved in aqueous methanol. The observed changes with methanol concentration, attributed to changes in coil conformation and to the helix-coil transition, represent a novel method of measuring polymer conformation. Polarization measurements as a function of temperature yield values of the energy differences between rotational isomeric states in the coil. deltaH, of 8.8 +/- 0.7, 10.4 +/- 1.1 and 10.8 +/- 1.5 kJ/mol at methanol concentrations (v/v) of 85, 80 and 70% respectively. The stabilization energy of the helix is estimated at 9.3 kJ/mol. PMID:949317

Synthesis of an N-aminopyrazinonium analogue of cytidine.

PubMed

Lee, T C; Chello, P L; Chou, T C; Templeton, M A; Parham, J C

1983-02-01

An N-aminated pyrazine analogue of cytidine, in which the pyrimidine N(3) ring nitrogen and C(4) amino group were replaced by a C-amino and an N-amino function, respectively, was prepared as a potential deaminase-resistant cytidine antimetabolite. The nucleoside 1,2-diamino-4-beta-D-ribofuranosylpyrazin-2-onium chloride (6) was a mild cytostatic agent but was neither a substrate for nor an inhibitor of mouse kidney cytidine deaminase. It ionized with a lower pKa than expected. The anion did not undergo the dimerization usually observed with N-imino heterocyclic ylides but unerwent hydrolysis of the 2-amino group to yield a 1-aminopyrazine-2,3-dione nucleoside.

Ion beam production and study of radioactive isotopes with the laser ion source at ISOLDE

NASA Astrophysics Data System (ADS)

Fedosseev, Valentin; Chrysalidis, Katerina; Day Goodacre, Thomas; Marsh, Bruce; Rothe, Sebastian; Seiffert, Christoph; Wendt, Klaus

2017-08-01

At ISOLDE the majority of radioactive ion beams are produced using the resonance ionization laser ion source (RILIS). This ion source is based on resonant excitation of atomic transitions by wavelength tunable laser radiation. Since its installation at the ISOLDE facility in 1994, the RILIS laser setup has been developed into a versatile remotely operated laser system comprising state-of-the-art solid state and dye lasers capable of generating multiple high quality laser beams at any wavelength in the range of 210-950 nm. A continuous programme of atomic ionization scheme development at CERN and at other laboratories has gradually increased the number of RILIS-ionized elements. At present, isotopes of 40 different elements have been selectively laser-ionized by the ISOLDE RILIS. Studies related to the optimization of the laser-atom interaction environment have yielded new laser ion source types: the laser ion source and trap and the versatile arc discharge and laser ion source. Depending on the specific experimental requirements for beam purity or versatility to switch between different ionization mechanisms, these may offer a favourable alternative to the standard hot metal cavity configuration. In addition to its main purpose of ion beam production, the RILIS is used for laser spectroscopy of radioisotopes. In an ongoing experimental campaign the isotope shifts and hyperfine structure of long isotopic chains have been measured by the extremely sensitive in-source laser spectroscopy method. The studies performed in the lead region were focused on nuclear deformation and shape coexistence effects around the closed proton shell Z = 82. The paper describes the functional principles of the RILIS, the current status of the laser system and demonstrated capabilities for the production of different ion beams including the high-resolution studies of short-lived isotopes and other applications of RILIS lasers for ISOLDE experiments. This article belongs to the Focus on Exotic Beams at ISOLDE: A Laboratory Portrait special issue.

On the ultrafast charge migration and subsequent charge directed reactivity in Cl⋯N halogen-bonded clusters following vertical ionization

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

Chandra, Sankhabrata; Bhattacharya, Atanu, E-mail: atanub@ipc.iisc.ernet.in; Periyasamy, Ganga

2015-06-28

In this article, we have presented ultrafast charge transfer dynamics through halogen bonds following vertical ionization of representative halogen bonded clusters. Subsequent hole directed reactivity of the radical cations of halogen bonded clusters is also discussed. Furthermore, we have examined effect of the halogen bond strength on the electron-electron correlation- and relaxation-driven charge migration in halogen bonded complexes. For this study, we have selected A-Cl (A represents F, OH, CN, NH{sub 2}, CF{sub 3}, and COOH substituents) molecules paired with NH{sub 3} (referred as ACl:NH{sub 3} complex): these complexes exhibit halogen bonds. To the best of our knowledge, this ismore » the first report on purely electron correlation- and relaxation-driven ultrafast (attosecond) charge migration dynamics through halogen bonds. Both density functional theory and complete active space self-consistent field theory with 6-31 + G(d, p) basis set are employed for this work. Upon vertical ionization of NCCl⋯NH{sub 3} complex, the hole is predicted to migrate from the NH{sub 3}-end to the ClCN-end of the NCCl⋯NH{sub 3} complex in approximately 0.5 fs on the D{sub 0} cationic surface. This hole migration leads to structural rearrangement of the halogen bonded complex, yielding hydrogen bonding interaction stronger than the halogen bonding interaction on the same cationic surface. Other halogen bonded complexes, such as H{sub 2}NCl:NH{sub 3}, F{sub 3}CCl:NH{sub 3}, and HOOCCl:NH{sub 3}, exhibit similar charge migration following vertical ionization. On the contrary, FCl:NH{sub 3} and HOCl:NH{sub 3} complexes do not exhibit any charge migration following vertical ionization to the D{sub 0} cation state, pointing to interesting halogen bond strength-dependent charge migration.« less

Ionizing radiation and taxonomic, functional and evolutionary diversity of bird communities.

PubMed

Morelli, Federico; Benedetti, Yanina; Mousseau, Timothy A; Møller, Anders Pape

2018-08-15

Ionizing radiation from nuclear accidents at Chernobyl, Fukushima and elsewhere has reduced the abundance, species richness and diversity of ecosystems. Here we analyzed the taxonomic, functional and evolutionary diversity of bird communities in forested areas around Chernobyl. Species richness decreased with increasing radiation, mainly in 2007. Functional richness, but not functional evenness and divergence, decreased with increasing level of ionizing radiation. Evolutionary distinctiveness of bird communities was higher in areas with higher levels of ionizing radiation. Regression tree models revealed that species richness was higher in bird communities in areas with radiation levels lower than 0.7 μSv/h. In contrast, when radiation levels were higher than 16.67 μSv/h, bird species richness reached a minimum. Functional richness was affected by two variables: Forest cover and radiation level. Higher functional richness was found in bird communities in areas with forest cover lower than 50%. In the areas with forest cover higher than 50%, the functional richness was lower when radiation level was higher than 0.91 μSv/h. Finally, the average evolutionary distinctiveness of bird communities was higher in areas with forest cover exceeding 50%. These findings imply that level of ionizing radiation interacted with forest cover to affect species richness and its component parts, i.e. taxonomic, functional, and evolutionary diversity. Copyright © 2018 Elsevier Ltd. All rights reserved.

Sperm quality and DNA damage in men from Jilin Province, China, who are occupationally exposed to ionizing radiation.

PubMed

Zhou, D D; Hao, J L; Guo, K M; Lu, C W; Liu, X D

2016-03-22

Long-term radiation exposure affects human health. Ionizing radiation has long been known to raise the risk of cancer. In addition to high doses of radiation, low-dose ionizing radiation might increase the risk of cardiovascular disease, lens opacity, and some other non-cancerous diseases. Low- and high-dose exposures to ionizing radiation elicit different signaling events at the molecular level, and may involve different response mechanisms. The health risks arising from exposure to low doses of ionizing radiation should be re-evaluated. Health workers exposed to ionizing radiation experience low-dose radiation and have an increased risk of hematological malignancies. Reproductive function is sensitive to changes in the physical environment, including ionizing radiation. However, data is scarce regarding the association between occupational radiation exposure and risk to human fertility. Sperm DNA integrity is a functional parameter of male fertility evaluation. Hence, we aimed to report sperm quality and DNA damage in men from Jilin Province, China, who were occupationally exposed to ionizing radiation. Sperm motility and normal morphology were significantly lower in the exposed compared with the non-exposed men. There was no statistically significant difference in sperm concentration between exposed and non-exposed men. The sperm DNA fragmentation index was significantly higher in the exposed than the non-exposed men. Chronic long-term exposure to low doses of ionizing radiation could affect sperm motility, normal morphology, and the sperm DNA fragmentation index in the Chinese population. Sperm quality and DNA integrity are functional parameters that could be used to evaluate occupational exposure to ionizing radiation.

QTAIM electron density study of natural chalcones

NASA Astrophysics Data System (ADS)

González Moa, María J.; Mandado, Marcos; Cordeiro, M. Natália D. S.; Mosquera, Ricardo A.

2007-09-01

QTAIM atomic and bond properties, ionization potential, and O-H bond dissociation energies calculated at the B3LYP/6-311++G(2d,2p) level indicate the natural chalcones bear a significant radical scavenging activity. However, their ionization potentials indicate they decrease the electron-transfer rate between antioxidant and oxygen that yields the pro-oxidative cations less than other natural antioxidants. Rings A and B display slight and similar positive charges, whereas ring B is involved in exocycle delocalization at a larger extension.

Measuring the effects of Coulomb repulsion via signal decay in an atmospheric pressure laser ionization ion mobility spectrometer.

PubMed

Ihlenborg, Marvin; Schuster, Ann-Kathrin; Grotemeyer, Juergen; Gunzer, Frank

2018-01-01

Using lasers in ion mobility spectrometry offers a lot of advantages compared to standard ionization sources. Especially, the ion yield can be drastically increased. It can, however, reach levels where the Coulomb repulsion leads to unwanted side effects. Here, we investigate how the Coulomb repulsion can be detected apart from the typical signal broadening by measuring effects created already in the reaction region and comparing them with corresponding finite element method simulations.

Communication: Strong laser alignment of solvent-solute aggregates in the gas-phase

NASA Astrophysics Data System (ADS)

Trippel, Sebastian; Wiese, Joss; Mullins, Terry; Küpper, Jochen

2018-03-01

Strong quasi-adiabatic laser alignment of the indole-water-dimer clusters, an amino-acid chromophore bound to a single water molecule through a hydrogen bond, was experimentally realized. The alignment was visualized through ion and electron imaging following strong-field ionization. Molecular-frame photoelectron angular distributions showed a clear suppression of the electron yield in the plane of the ionizing laser's polarization, which was analyzed as strong alignment of the molecular cluster with ⟨cos2 θ2D⟩ ≥ 0.9.

Orientation dependent ionization potential of In2O3: a natural source for inhomogeneous barrier formation at electrode interfaces in organic electronics.

PubMed

Hohmann, Mareike V; Ágoston, Péter; Wachau, André; Bayer, Thorsten J M; Brötz, Joachim; Albe, Karsten; Klein, Andreas

2011-08-24

The ionization potentials of In(2)O(3) films grown epitaxially by magnetron sputtering on Y-stabilized ZrO(2) substrates with (100) and (111) surface orientation are determined using photoelectron spectroscopy. Epitaxial growth is verified using x-ray diffraction. The observed ionization potentials, which directly affect the work functions, are in good agreement with ab initio calculations using density functional theory. While the (111) surface exhibits a stable surface termination with an ionization potential of ∼ 7.0 eV, the surface termination and the ionization potential of the (100) surface depend strongly on the oxygen chemical potential. With the given deposition conditions an ionization potential of ∼ 7.7 eV is obtained, which is attributed to a surface termination stabilized by oxygen dimers. This orientation dependence also explains the lower ionization potentials observed for In(2)O(3) compared to Sn-doped In(2)O(3) (ITO) (Klein et al 2009 Thin Solid Films 518 1197-203). Due to the orientation dependent ionization potential, a polycrystalline ITO film will exhibit a laterally varying work function, which results in an inhomogeneous charge injection into organic semiconductors when used as electrode material. The variation of work function will become even more pronounced when oxygen plasma or UV-ozone treatments are performed, as an oxidation of the surface is only possible for the (100) surface. The influence of the deposition technique on the formation of stable surface terminations is also discussed. © 2011 IOP Publishing Ltd

Qualitative and quantitative analysis of poly(amidoamine) dendrimers in an aqueous matrix by liquid chromatography-electrospray ionization-hybrid quadrupole/time-of-flight mass spectrometry (LC-ESI-QTOF-MS).

PubMed

Uclés, A; Ulaszewska, M M; Hernando, M D; Ramos, M J; Herrera, S; García, E; Fernández-Alba, A R

2013-07-01

This work introduces a liquid chromatography-electrospray ionization-hybrid quadrupole/time-of-flight mass spectrometry (LC-ESI-QTOF-MS)-based method for qualitative and quantitative analysis of poly(amidoamine) (PAMAM) dendrimers of generations 0 to 3 in an aqueous matrix. The multiple charging of PAMAM dendrimers generated by means of ESI has provided key advantages in dendrimer identification by assignation of charge state through high resolution of isotopic clusters. Isotopic distribution in function of abundance of isotopes (12)C and (13)C yielded valuable and complementarity data for confident characterization. A mass accuracy below 3.8 ppm for the most abundant isotopes (diagnostic ions) provided unambiguous identification of PAMAM dendrimers. Validation of the LC-ESI-QTOF-MS method and matrix effect evaluation enabled reliable and reproducible quantification. The validation parameters, limits of quantification in the range of 0.012 to 1.73 μM, depending on the generation, good linear range (R > 0.996), repeatability (RSD < 13.4%), and reproducibility (RSD < 10.9%) demonstrated the suitability of the method for the quantification of dendrimers in aqueous matrices (water and wastewater). The added selectivity, achieved by multicharge phenomena, represents a clear advantage in screening aqueous mixtures due to the fact that the matrix had no significant effect on ionization, with what is evidenced by an absence of sensitivity loss in most generations of PAMAM dendrimers. Fig Liquid chromatography-electrospray ionization-hybrid quadrupole/time of flight mass spectrometry (LC-ESI-QTOF-MS) based method for qualitative and quantitative analysis of PAMAM dendrimers in aqueous matrix.

Electronic Properties and Dissociative Photoionization of Thiocyanates, Part III. The Effect of the Group's Electronegativity in the Valence and Shallow-Core (Sulfur and Chlorine 2p) Regions of CCl3SCN and CCl2FSCN.

PubMed

Rodríguez Pirani, Lucas S; Della Védova, Carlos O; Geronés, Mariana; Romano, Rosana M; Cavasso-Filho, Reinaldo; Ge, Maofa; Ma, Chunping; Erben, Mauricio F

2017-12-07

Both photoelectron spectroscopy (PES) data and PhotoElectron-PhotoIon-Coincidence (PEPICO) spectra obtained from a synchrotron facility have been used to examine the electronic structure and the dissociative ionization of halomethyl thiocyantes in the valence and shallow-core S 2p and Cl 2p regions. Two simple and closely related molecules, namely, CCl 3 SCN and CCl 2 FSCN, have been analyzed to assess the role of halogen substitution in the electronic properties of thiocyanates. The assignment of the He(I) photoelectron spectra has been achieved with the help of quantum chemical calculations at the outer-valence Green's function (OVGF) level of approximation. The first ionization energies observed at 10.55 and 10.78 eV for CCl 3 SCN and CCl 2 FSCN, respectively, are assigned to ionization processes from the sulfur lone pair orbital [n(S)]. When these molecules are compared with CX 3 SCN (X = H, Cl, F) species, a linear relationship between the vertical first ionization energy and electronegativity of CX 3 group is observed. Irradiation of CCl 3 SCN and CCl 2 FSCN with photons in the valence energy regions leads to the formation of CCl 2 X + and CClXSCN + ions (X = Cl or F). Additionally, the achievement of the fragmentation patterns and the total ion yield spectra obtained from the PEPICO data in the S 2p and Cl 2p regions and several dissociation channels can be inferred for the core-excited species by using the triple coincidence PEPIPICO (PhotoElectron-PhotoIon-PhotoIon-Coincidence) spectra.

Influence of hadron and atmospheric models on computation of cosmic ray ionization in the atmosphere-Extension to heavy nuclei

NASA Astrophysics Data System (ADS)

Mishev, A. L.; Velinov, P. I. Y.

2014-12-01

In the last few years an essential progress in development of physical models for cosmic ray induced ionization in the atmosphere is achieved. The majority of these models are full target, i.e. based on Monte Carlo simulation of an electromagnetic-muon-nucleon cascade in the atmosphere. Basically, the contribution of proton nuclei is highlighted, i.e. the contribution of primary cosmic ray α-particles and heavy nuclei to the atmospheric ionization is neglected or scaled to protons. The development of cosmic ray induced atmospheric cascade is sensitive to the energy and mass of the primary cosmic ray particle. The largest uncertainties in Monte Carlo simulations of a cascade in the Earth atmosphere are due to assumed hadron interaction models, the so-called hadron generators. In the work presented here we compare the ionization yield functions Y for primary cosmic ray nuclei, such as α-particles, Oxygen and Iron nuclei, assuming different hadron interaction models. The computations are fulfilled with the CORSIKA 6.9 code using GHEISHA 2002, FLUKA 2011, UrQMD hadron generators for energy below 80 GeV/nucleon and QGSJET II for energy above 80 GeV/nucleon. The observed difference between hadron generators is widely discussed. The influence of different atmospheric parametrizations, namely US standard atmosphere, US standard atmosphere winter and summer profiles on ion production rate is studied. Assuming realistic primary cosmic ray mass composition, the ion production rate is obtained at several rigidity cut-offs - from 1 GV (high latitudes) to 15 GV (equatorial latitudes) using various hadron generators. The computations are compared with experimental data. A conclusion concerning the consistency of the hadron generators is stated.

Effect of an InxGa1-xAs-GaAs blocking heterocathode metal contact on the GaAs TED operation

NASA Astrophysics Data System (ADS)

Arkusha, Yu. V.; Prokhorov, E. D.; Storozhenko, I. P.

2004-09-01

The frequency dependence of the generation efficiency of an mm- -nn:In:InxGaGa1-1-xAs- As-nn:GaAs-:GaAs-nn++:GaAs TED with the 2.5-mm long active region is calculated. The optimum values - which yield the diode maximum generation efficiency - for the :GaAs TED with the 2.5-mm long active region is calculated. The optimum values - which yield the diode maximum generation efficiency - for the nn:In:InxGaGa1-1-xAs cathode length, the cathode concentration of ionized impurities, and the height of the potential barrier on metal contact are determined.As cathode length, the cathode concentration of ionized impurities, and the height of the potential barrier on metal contact are determined.

Biomolecular damage induced by ionizing radiation: the direct and indirect effects of low-energy electrons on DNA.

PubMed

Alizadeh, Elahe; Orlando, Thomas M; Sanche, Léon

2015-04-01

Many experimental and theoretical advances have recently allowed the study of direct and indirect effects of low-energy electrons (LEEs) on DNA damage. In an effort to explain how LEEs damage the human genome, researchers have focused efforts on LEE interactions with bacterial plasmids, DNA bases, sugar analogs, phosphate groups, and longer DNA moieties. Here, we summarize the current understanding of the fundamental mechanisms involved in LEE-induced damage of DNA and complex biomolecule films. Results obtained by several laboratories on films prepared and analyzed by different methods and irradiated with different electron-beam current densities and fluencies are presented. Despite varied conditions (e.g., film thicknesses and morphologies, intrinsic water content, substrate interactions, and extrinsic atmospheric compositions), comparisons show a striking resemblance in the types of damage produced and their yield functions. The potential of controlling this damage using molecular and nanoparticle targets with high LEE yields in targeted radiation-based cancer therapies is also discussed.

Photoabsorption of the molecular IH cation at the iodine 3 d absorption edge

NASA Astrophysics Data System (ADS)

Klumpp, Stephan; Guda, Alexander A.; Schubert, Kaja; Mertens, Karolin; Hellhund, Jonas; Müller, Alfred; Schippers, Stefan; Bari, Sadia; Martins, Michael

2018-03-01

Yields of atomic iodine Iq + (q ≥2 ) fragments resulting from photoexcitation and photoionization of the target ions IH+ and I+ have been measured in the photon-energy range 610-680 eV, which comprises the thresholds for iodine 3 d ionization. The measured ion-yield spectra show two strong and broad resonance features due to the excitation of the 3 d3 /2 ,5 /2 electrons into ɛ f states rather similar for both parent ions. In the 3 d pre-edge range, excitations into (n p π ) -like orbitals and into an additional σ* orbital are found for IH+, which have been identified by comparison of the atomic I+ and molecular IH+ data and with the help of (time-dependent) density functional theory (DFT) and atomic Hartree-Fock calculations. The (5 p π ) orbital is almost atomlike, whereas all other resonances of the IH+ primary ion show a more pronounced molecular character, which is deduced from the chemical shifts of the resonances and the theoretical analysis.

Detection limits of organic compounds achievable with intense, short-pulse lasers.

PubMed

Miles, Jordan; De Camillis, Simone; Alexander, Grace; Hamilton, Kathryn; Kelly, Thomas J; Costello, John T; Zepf, Matthew; Williams, Ian D; Greenwood, Jason B

2015-06-21

Many organic molecules have strong absorption bands which can be accessed by ultraviolet short pulse lasers to produce efficient ionization. This resonant multiphoton ionization scheme has already been exploited as an ionization source in time-of-flight mass spectrometers used for environmental trace analysis. In the present work we quantify the ultimate potential of this technique by measuring absolute ion yields produced from the interaction of 267 nm femtosecond laser pulses with the organic molecules indole and toluene, and gases Xe, N2 and O2. Using multiphoton ionization cross sections extracted from these results, we show that the laser pulse parameters required for real-time detection of aromatic molecules at concentrations of one part per trillion in air and a limit of detection of a few attomoles are achievable with presently available commercial laser systems. The potential applications for the analysis of human breath, blood and tissue samples are discussed.

Measuring Ionization in Highly Compressed, Near-Degenerate Plasmas

NASA Astrophysics Data System (ADS)

Doeppner, Tilo; Kraus, D.; Neumayer, P.; Bachmann, B.; Collins, G. W.; Divol, L.; Kritcher, A.; Landen, O. L.; Pak, A.; Weber, C.; Fletcher, L.; Glenzer, S. H.; Falcone, R. W.; Saunders, A.; Chapman, D.; Baggott, R.; Gericke, D. O.; Yi, A.

2016-10-01

A precise knowledge of ionization at given temperature and density is required to accurately model compressibility and heat capacity of materials at extreme conditions. We use x-ray Thomson scattering to characterize the plasma conditions in plastic and beryllium capsules near stagnation in implosion experiments at the National Ignition Facility. We expect the capsules to be compressed to more than 20x and electron densities approaching 1025 cm-3, corresponding to a Fermi energy of 170 eV. Zinc Heα x-rays (9 keV) scattering at 120° off the plasma yields high sensitivity to K-shell ionization, while at the same time constraining density and temperature. We will discuss recent results in the context of ionization potential depression at these extreme conditions. This work was performed under the auspices of the US Department of Energy by Lawrence Livermore National Laboratory under Contract DE-AC52-07NA27344.

MESSENGER observations of the composition of Mercury's ionized exosphere and plasma environment.

PubMed

Zurbuchen, Thomas H; Raines, Jim M; Gloeckler, George; Krimigis, Stamatios M; Slavin, James A; Koehn, Patrick L; Killen, Rosemary M; Sprague, Ann L; McNutt, Ralph L; Solomon, Sean C

2008-07-04

The region around Mercury is filled with ions that originate from interactions of the solar wind with Mercury's space environment and through ionization of its exosphere. The MESSENGER spacecraft's observations of Mercury's ionized exosphere during its first flyby yielded Na+, O+, and K+ abundances, consistent with expectations from observations of neutral species. There are increases in ions at a mass per charge (m/q) = 32 to 35, which we interpret to be S+ and H2S+, with (S+ + H2S+)/(Na+ + Mg+) = 0.67 +/- 0.06, and from water-group ions around m/q = 18, at an abundance of 0.20 +/- 0.03 relative to Na+ plus Mg+. The fluxes of Na+, O+, and heavier ions are largest near the planet, but these Mercury-derived ions fill the magnetosphere. Doubly ionized ions originating from Mercury imply that electrons with energies less than 1 kiloelectron volt are substantially energized in Mercury's magnetosphere.

Single and multiple ionization of C{sub 60} fullerenes and collective effects in collisions with highly charged C, F, and Si ions with energy 3 MeV/u

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

Kelkar, A. H.; Kadhane, U.; Misra, D.

2010-10-15

We have measured absolute cross sections for single, double, triple, and quadruple ionization of C{sub 60} in collisions with 3 MeV/u C, F, and Si projectile ions at various projectile charge states. The experiment was performed using the recoil-ion time-of-flight technique. Projectile charge state dependence of the ionization yields was compared mainly with a model based on the giant dipole plasmon resonance (GDPR). In some cases, the continuum-distorted-wave-eikonal-initial-state (CDW-EIS) model which is normally applied for ion-atom collisions was also used as a reference. An excellent qualitative agreement between the experimental data for single and double ionization and the GDPR modelmore » predictions was found for all projectile charge states.« less

Time-dependent density-functional theory with optimized effective potential and self-interaction correction and derivative discontinuity for the treatment of double ionization of He and Be atoms in intense laser fields

NASA Astrophysics Data System (ADS)

Heslar, John; Telnov, Dmitry A.; Chu, Shih-I.

2013-05-01

We present a self-interaction-free time-dependent density-functional theory (TDDFT) for the treatment of double-ionization processes of many-electron systems. The method is based on the extension of the Krieger-Li-Iafrate (KLI) treatment of the optimized effective potential (OEP) theory and the incorporation of an explicit self-interaction correction (SIC) term. In the framework of the time-dependent density functional theory, we have performed three-dimensional (3D) calculations of double ionization of He and Be atoms by intense near-infrared laser fields. We make use of the exchange-correlation potential with the integer discontinuity which improves the description of the double-ionization process. We found that a proper description of the double ionization requires the TDDFT exchange-correlation potential with the discontinuity with respect to the variation of the total particle number (TPN). The results for the intensity-dependent rates of double ionization of He and Be atoms are presented.

Application of Ni-63 photo and corona discharge ionization for the analysis of chemical warfare agents and toxic wastes

NASA Technical Reports Server (NTRS)

Stach, J.; Adler, J.; Brodacki, M.; Doring, H.-R.

1995-01-01

Over the past decade, advances in instrumental design and refinements in the understanding of ion molecule reactions at atmospheric pressure enabled the application of Ion Mobility Spectrometry (IMS) as a simple inexpensive and sensitive analytical method for the detection of organic trace compounds. Positive and negative gas-phase ions for ion mobility spectrometry have been produced by a variety of methods, including photo-ionization, laser multi photon ionization, surface ionization, corona discharge ionization. The most common ion source used in ion mobility spectrometry is a radioactive Ni-63 foil which is favored due to simplicity, stability, convenience, and high selectivity. If reactant ions like (H2O(n)H)(+) or (H2O(n)O2)(-) dominate in the reaction region, nearly all kinds of compounds with a given proton or electron affinity; are ionized. However, the radioactivity of the Ni-63 foil is one disadvantage of this ion source that stimulates the development and application of other ionization techniques. In this paper, we report analyses of old chemical warfare agents and toxic wastes using Bruker RAID ion mobility spectrometers. Due to the modular construction of the measuring cell, the spectrometers can be equipped with different ion sources. The combined use of Ni-63, photo- and corona discharge ionization allows the identification of different classes of chemical compounds and yields in most cases comparable results.

Capillary atmospheric pressure electron capture ionization (cAPECI): a highly efficient ionization method for nitroaromatic compounds.

PubMed

Derpmann, Valerie; Mueller, David; Bejan, Iustinian; Sonderfeld, Hannah; Wilberscheid, Sonja; Koppmann, Ralf; Brockmann, Klaus J; Benter, Thorsten

2014-03-01

We report on a novel method for atmospheric pressure ionization of compounds with elevated electron affinity (e.g., nitroaromatic compounds) or gas phase acidity (e.g., phenols), respectively. The method is based on the generation of thermal electrons by the photo-electric effect, followed by electron capture of oxygen when air is the gas matrix yielding O2(-) or of the analyte directly with nitrogen as matrix. Charge transfer or proton abstraction by O2(-) leads to the ionization of the analytes. The interaction of UV-light with metals is a clean method for the generation of thermal electrons at atmospheric pressure. Furthermore, only negative ions are generated and neutral radical formation is minimized, in contrast to discharge- or dopant assisted methods. Ionization takes place inside the transfer capillary of the mass spectrometer leading to comparably short transfer times of ions to the high vacuum region of the mass spectrometer. This strongly reduces ion transformation processes, resulting in mass spectra that more closely relate to the neutral analyte distribution. cAPECI is thus a soft and selective ionization method with detection limits in the pptV range. In comparison to standard ionization methods (e.g., PTR), cAPECI is superior with respect to both selectivity and achievable detection limits. cAPECI demonstrates to be a promising ionization method for applications in relevant fields as, for example, explosives detection and atmospheric chemistry.

Production of N(+)-asterisk from N2 + hnu - Effective EUV emission yields from laboratory and dayglow data

NASA Technical Reports Server (NTRS)

Meier, R. R.; Samson, James A. R.; Chung, Y.; Lee, E.-M.; He, Z.-X.

1991-01-01

Photodissociative ionization of N2 into the unbound N2(+) H 2Sigma-g(+) state is identified as the parentage of a number of N(+) and N-excited states that contribute to the u.v. dayglow. Yields have been obtained for the production of extreme ultraviolet emission lines of N(+) and N from a laboratory experiment using a broadband synchrotron radiation source with fluorescence spectroscopy. The yields are termed 'effective', in that they are constant percentages of the H state cross section. These are compared wih effective yields needed to reproduce N II 1085 and 916 A lines from four dayglow observations using a model of solar energy deposition and photoelectron production and loss in the earth's thermosphere. The 1085 A effective yield measured in the laboratory (18 percent) agrees with that from the dayglow data (average of 17 percent) to well within experimental uncertainties. Thus, it is concluded that photodissociative ionization of N2 is the primary source of the N II 1085 A dayglow. However, there is an order of magnitude discrepancy among the various dayglow observations of the 1085/916 intensity ratio, only one of which is consistent with the laboratory observation of 4.4. Neither contamination by other dayglow features nor atmospheric extinction can account for the disparities. Laboratory measurements of N2 and O2 absorption cross sections at these wavelengths are also reported.

Intact and Top-Down Characterization of Biomolecules and Direct Analysis Using Infrared Matrix-Assisted Laser Desorption Electrospray Ionization Coupled to FT-ICR Mass Spectrometry

PubMed Central

Sampson, Jason S.; Murray, Kermit K.; Muddiman, David C.

2013-01-01

We report the implementation of an infrared laser onto our previously reported matrix-assisted laser desorption electrospray ionization (MALDESI) source with ESI post-ionization yielding multiply charged peptides and proteins. Infrared (IR)-MALDESI is demonstrated for atmospheric pressure desorption and ionization of biological molecules ranging in molecular weight from 1.2 to 17 kDa. High resolving power, high mass accuracy single-acquisition Fourier transform ion cyclotron resonance (FT-ICR) mass spectra were generated from liquid-and solid-state peptide and protein samples by desorption with an infrared laser (2.94 µm) followed by ESI post-ionization. Intact and top-down analysis of equine myoglobin (17 kDa) desorbed from the solid state with ESI post-ionization demonstrates the sequencing capabilities using IR-MALDESI coupled to FT-ICR mass spectrometry. Carbohydrates and lipids were detected through direct analysis of milk and egg yolk using both UV- and IR-MALDESI with minimal sample preparation. Three of the four classes of biological macromolecules (proteins, carbohydrates, and lipids) have been ionized and detected using MALDESI with minimal sample preparation. Sequencing of O-linked glycans, cleaved from mucin using reductive β-elimination chemistry, is also demonstrated. PMID:19185512

Trace detection of organic compounds in complex sample matrixes by single photon ionization ion trap mass spectrometry: real-time detection of security-relevant compounds and online analysis of the coffee-roasting process.

PubMed

Schramm, Elisabeth; Kürten, Andreas; Hölzer, Jasper; Mitschke, Stefan; Mühlberger, Fabian; Sklorz, Martin; Wieser, Jochen; Ulrich, Andreas; Pütz, Michael; Schulte-Ladbeck, Rasmus; Schultze, Rainer; Curtius, Joachim; Borrmann, Stephan; Zimmermann, Ralf

2009-06-01

An in-house-built ion trap mass spectrometer combined with a soft ionization source has been set up and tested. As ionization source, an electron beam pumped vacuum UV (VUV) excimer lamp (EBEL) was used for single-photon ionization. It was shown that soft ionization allows the reduction of fragmentation of the target analytes and the suppression of most matrix components. Therefore, the combination of photon ionization with the tandem mass spectrometry (MS/MS) capability of an ion trap yields a powerful tool for molecular ion peak detection and identification of organic trace compounds in complex matrixes. This setup was successfully tested for two different applications. The first one is the detection of security-relevant substances like explosives, narcotics, and chemical warfare agents. One test substance from each of these groups was chosen and detected successfully with single photon ionization ion trap mass spectrometry (SPI-ITMS) MS/MS measurements. Additionally, first tests were performed, demonstrating that this method is not influenced by matrix compounds. The second field of application is the detection of process gases. Here, exhaust gas from coffee roasting was analyzed in real time, and some of its compounds were identified using MS/MS studies.

On the SIMS Ionization Probability of Organic Molecules.

PubMed

Popczun, Nicholas J; Breuer, Lars; Wucher, Andreas; Winograd, Nicholas

2017-06-01

The prospect of improved secondary ion yields for secondary ion mass spectrometry (SIMS) experiments drives innovation of new primary ion sources, instrumentation, and post-ionization techniques. The largest factor affecting secondary ion efficiency is believed to be the poor ionization probability (α + ) of sputtered material, a value rarely measured directly, but estimated to be in some cases as low as 10 -5 . Our lab has developed a method for the direct determination of α + in a SIMS experiment using laser post-ionization (LPI) to detect neutral molecular species in the sputtered plume for an organic compound. Here, we apply this method to coronene (C 24 H 12 ), a polyaromatic hydrocarbon that exhibits strong molecular signal during gas-phase photoionization. A two-dimensional spatial distribution of sputtered neutral molecules is measured and presented. It is shown that the ionization probability of molecular coronene desorbed from a clean film under bombardment with 40 keV C 60 cluster projectiles is of the order of 10 -3 , with some remaining uncertainty arising from laser-induced fragmentation and possible differences in the emission velocity distributions of neutral and ionized molecules. In general, this work establishes a method to estimate the ionization efficiency of molecular species sputtered during a single bombardment event. Graphical Abstract .

Ionization, photoelectron dynamics and elastic scattering in relativistic, ultra-strong field

NASA Astrophysics Data System (ADS)

Luo, Sui

Ultrastrong laser-matter interaction has direct bearing to next generation technologies including plasma acceleration, laser fusion and attosecond X-ray generation. The commonly known physics in strong field becomes different as one progress to ultrastrong field. The works presented in this dissertation theoretically study the influence of relativistic effect and magnetic component of the laser field on the ionization, photoelectron dynamics and elastic scattering processes. The influence of magnetic component (B laser) of circularly polarized (CP) ultrastrong fields (up to3 x 1022 W/cm2) on atomic bound state dynamics is investigated. The Poincare plots are used to find the changes in trajectory energies are on the order of a few percent for intensities up to1 x 1022 W/cm2. It is found that at intensities where ionization approaches 50% for the bound state, the small changes from Blaser of the circular polarized light can actually result in a several-fold decrease in ionization probability. The force on the bound electron exerted by the Lorentz force from B laser is perpendicular to the rotating plane of the circular polarized light, and this nature makes those trajectories which are aligned away from the minimum in the potential barrier stabilized against tunneling ionization. Our results provide a classical understanding for ionization in ultrastrong fields and indicate that relativistic effects in ultrastrong field ionization may most easily be seen with CP fields. The photoelectron energy spectra from elastic rescattering in ultrastrong laser fields (up to 2x1019 W/cm2) is studied by using a relativistic adaption of a semi-classical three-step recollision model. The Hartree-Fock scattering potentials are used in calculating the elastic rescattering for both hydrogenlike and noble gas species. It is found that there is a reduction in elastic rescattering for intensities beyond 6 x 1016 W/cm2 when the laser Lorentz deflection of the photoelectron exceeds its wave-function spread. A relativistic rescattering enhancement occurs at 2 x 1018 W/cm2, commensurate with relativistic motion of a classical electron in a single field cycle. The good comparison between the results with available experiments suggests the theory approach is well suited to modeling scattering in the ultrastrong intensity regime. We investigate the elastic scattering process as it changes from strong to ultrastrong fields with the photoelectron angular distributions from Ne, Ar, and Xe. Noble gas species with Hartree-Fock scattering potentials show a reduction in elastic rescattering with the increasing energy of ultrastrong fields. It is found that as one increases the returning photoelectron energy, rescattering becomes the dominating mechanism behind the yield distribution as the emission angle for all the species extends from 0° to 90°. The relativistic effects and the magnetic field do not change the angular distribution until one is well into the Gamma r "1 regime where the Lorentz defection significantly reduces the yield. As we proceed to the highest energy, the angular emission range narrows as the mechanism changes over to backscattering into narrow angles along the electric field.

Accurate potentiometric determination of lipid membrane-water partition coefficients and apparent dissociation constants of ionizable drugs: electrostatic corrections.

PubMed

Elsayed, Mustafa M A; Vierl, Ulrich; Cevc, Gregor

2009-06-01

Potentiometric lipid membrane-water partition coefficient studies neglect electrostatic interactions to date; this leads to incorrect results. We herein show how to account properly for such interactions in potentiometric data analysis. We conducted potentiometric titration experiments to determine lipid membrane-water partition coefficients of four illustrative drugs, bupivacaine, diclofenac, ketoprofen and terbinafine. We then analyzed the results conventionally and with an improved analytical approach that considers Coulombic electrostatic interactions. The new analytical approach delivers robust partition coefficient values. In contrast, the conventional data analysis yields apparent partition coefficients of the ionized drug forms that depend on experimental conditions (mainly the lipid-drug ratio and the bulk ionic strength). This is due to changing electrostatic effects originating either from bound drug and/or lipid charges. A membrane comprising 10 mol-% mono-charged molecules in a 150 mM (monovalent) electrolyte solution yields results that differ by a factor of 4 from uncharged membranes results. Allowance for the Coulombic electrostatic interactions is a prerequisite for accurate and reliable determination of lipid membrane-water partition coefficients of ionizable drugs from potentiometric titration data. The same conclusion applies to all analytical methods involving drug binding to a surface.

Molecular interferometer to decode attosecond electron-nuclear dynamics.

PubMed

Palacios, Alicia; González-Castrillo, Alberto; Martín, Fernando

2014-03-18

Understanding the coupled electronic and nuclear dynamics in molecules by using pump-probe schemes requires not only the use of short enough laser pulses but also wavelengths and intensities that do not modify the intrinsic behavior of the system. In this respect, extreme UV pulses of few-femtosecond and attosecond durations have been recognized as the ideal tool because their short wavelengths ensure a negligible distortion of the molecular potential. In this work, we propose the use of two twin extreme UV pulses to create a molecular interferometer from direct and sequential two-photon ionization processes that leave the molecule in the same final state. We theoretically demonstrate that such a scheme allows for a complete identification of both electronic and nuclear phases in the wave packet generated by the pump pulse. We also show that although total ionization yields reveal entangled electronic and nuclear dynamics in the bound states, doubly differential yields (differential in both electronic and nuclear energies) exhibit in addition the dynamics of autoionization, i.e., of electron correlation in the ionization continuum. Visualization of such dynamics is possible by varying the time delay between the pump and the probe pulses.

A thermal extrapolation method for the effective temperatures and internal energies of activated ions

NASA Astrophysics Data System (ADS)

Meot-Ner (Mautner), Michael; Somogyi, Árpád

2007-11-01

The internal energies of dissociating ions, activated chemically or collisionally, can be estimated using the kinetics of thermal dissociation. The thermal Arrhenius parameters can be combined with the observed dissociation rate of the activated ions using kdiss = Athermalexp(-Ea,thermal/RTeff). This Arrhenius-type relation yields the effective temperature, Teff, at which the ions would dissociate thermally at the same rate, or yield the same product distributions, as the activated ions. In turn, Teff is used to calculate the internal energy of the ions and the energy deposited by the activation process. The method yields an energy deposition efficiency of 10% for a chemical ionization proton transfer reaction and 8-26% for the surface collisions of various peptide ions. Internal energies of ions activated by chemical ionization or by gas phase collisions, and of ions produced by desorption methods such as fast atom bombardment, can be also evaluated. Thermal extrapolation is especially useful for ion-molecule reaction products and for biological ions, where other methods to evaluate internal energies are laborious or unavailable.

Phase-dependent above-barrier ionization of excited-state electrons.

PubMed

Yang, Weifeng; Song, Xiaohong; Chen, Zhangjin

2012-05-21

The carrier-envelope phase (CEP)-dependent above-barrier ionization (ABI) has been investigated in order to probe the bound-state electron dynamics. It is found that when the system is initially prepared in the excited state, the ionization yield asymmetry between left and right sides can occur both in low-energy and high-energy parts of the photoelectron spectra. Moreover, in electron momentum map, a new interference effect along the direction perpendicular to the laser polarization is found. We show that this interference is related to the competition among different excited states. The interference effect is dependent on CEPs of few-cycle probe pulses, which can be used to trace the superposition information and control the electron wave packet of low excited states.

Enhanced production of low energy electrons by alpha particle impact

PubMed Central

Kim, Hong-Keun; Titze, Jasmin; Schöffler, Markus; Trinter, Florian; Waitz, Markus; Voigtsberger, Jörg; Sann, Hendrik; Meckel, Moritz; Stuck, Christian; Lenz, Ute; Odenweller, Matthias; Neumann, Nadine; Schössler, Sven; Ullmann-Pfleger, Klaus; Ulrich, Birte; Fraga, Rui Costa; Petridis, Nikos; Metz, Daniel; Jung, Annika; Grisenti, Robert; Czasch, Achim; Jagutzki, Ottmar; Schmidt, Lothar; Jahnke, Till; Schmidt-Böcking, Horst; Dörner, Reinhard

2011-01-01

Radiation damage to living tissue stems not only from primary ionizing particles but to a substantial fraction from the dissociative attachment of secondary electrons with energies below the ionization threshold. We show that the emission yield of those low energy electrons increases dramatically in ion–atom collisions depending on whether or not the target atoms are isolated or embedded in an environment. Only when the atom that has been ionized and excited by the primary particle impact is in immediate proximity of another atom is a fragmentation route known as interatomic Coulombic decay (ICD) enabled. This leads to the emission of a low energy electron. Over the past decade ICD was explored in several experiments following photoionization. Most recent results show its observation even in water clusters. Here we show the quantitative role of ICD for the production of low energy electrons by ion impact, thus approaching a scenario closer to that of radiation damage by alpha particles: We choose ion energies on the maximum of the Bragg peak where energy is most efficiently deposited in tissue. We compare the electron production after colliding He+ ions on isolated Ne atoms and on Ne dimers (Ne2). In the latter case the Ne atom impacted is surrounded by a most simple environment already opening ICD as a deexcitation channel. As a consequence, we find a dramatically enhanced low energy electron yield. The results suggest that ICD may have a significant influence on cell survival after exposure to ionizing radiation. PMID:21730184

SU-F-T-174: Patient-Specific Point Dose Measurement Using Fiber Optic Radiation Sensor Using Cerenkov Radiation for Proton Therapeutic Beam

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

Son, J; National Cancer Center, Goyang-si; Kim, M

Purpose: A fiber-optic radiation sensor using Cerenkov radiation (FOCR) has been widely studied for use as a dosimeter for proton therapeutic beam. We developed the FOCR, and it applied to patient-specific point dose measurement in order to evaluate the effectiveness of the FOCR system for proton therapy QA. Methods: Calibration of FOCR was performed with an ionization chamber whose absolute doses were determined according to the IAEA TRS-398 protocol. To determine the calibration curve, the FOCR was irradiated perpendicularly to the proton beam at the 13 dose levels steps. We selected five actual patient treatment plans performed at proton therapymore » center and compared the resulting FOCR measurements with the ionization chamber measurements. Results: The Cerenkov light yield of the FOCR increases linearly with as the dose measured using the ionization chamber increases from 0 cGy to 500 cGy. The results indicate that the fitting curve is linear, suggesting that dose measurement based on the light yield of the FOCR is possible. The results of proton radiation dose QA performed using the FOCR for 10 proton fields and five patients are good agreement with an ionization chamber. Conclusion: We carried out the patient QA using the FOCR for proton therapeutic beam and evaluated the effectiveness of the FOCR as a proton therapy QA tool. Our results indicate that the FOCR is suitable for use in patient QA of clinical proton beams.« less

Ionization Cross Sections and Dissociation Channels of DNA Bases by Electron Collisions

NASA Technical Reports Server (NTRS)

Huo, Winifred M.; Dateo, Christopher E.; Fletcher, Graham D.

2004-01-01

Free secondary electrons are the most abundant secondary species in ionizing radiation. Their role in DNA damage, both direct and indirect, is an active area of research. While indirect damage by free radicals, particularly by the hydroxyl radical generated by electron collision with water. is relatively well studied, damage by direct electron collision with DNA is less well understood. Only recently Boudaiffa et al. demonstrated that electrons at energies well below ionization thresholds can induce substantial yields of single- and double-strand breaks in DNA by a resonant, dissociative attachment process. This study attracted renewed interest in electron collisions with DNA, especially in the low energy region. At higher energies ionization becomes important. While Monte Carlo track simulations of radiation damage always include ionization, the probability of dissociative ionization, i.e., simultaneous ionization and dissociation, is ignored. Just like dissociative attachment, dissociative ionization may be an important contributor to double-strand breaks since the radicals and ions produced by dissociative ionization, located in the vicinity of the DNA coil, can readily interact with other parts of the DNA. Using the improved binary-encounter dipole (iBED) formulation, we calculated the ionization cross sections of the four DNA bases, adenine, cytosine, guanine, and thymine, by electrons at energies from threshold to 1 KeV. The present calculation gives cross sections approximately 20% lower than the results by Bemhardt and Paretzke using the Deutsch-Mark and Binary-Encounter-Bethe (BEB) formalisms. The difference is most likely due to the lack of a shielding term in the dipole potential used in the Deutsch-Mark and BEB formalisms. The dissociation channels of ionization for the bases are currently being studied.

Two-body loss rates for reactive collisions of cold atoms

NASA Astrophysics Data System (ADS)

Cop, C.; Walser, R.

2018-01-01

We present an effective two-channel model for reactive collisions of cold atoms. It augments elastic molecular channels with an irreversible, inelastic loss channel. Scattering is studied with the distorted-wave Born approximation and yields general expressions for angular momentum resolved cross sections as well as two-body loss rates. Explicit expressions are obtained for piecewise constant potentials. A pole expansion reveals simple universal shape functions for cross sections and two-body loss rates in agreement with the Wigner threshold laws. This is applied to collisions of metastable 20Ne and 21Ne atoms, which decay primarily through exothermic Penning or associative ionization processes. From a numerical solution of the multichannel Schrödinger equation using the best currently available molecular potentials, we have obtained synthetic scattering data. Using the two-body loss shape functions derived in this paper, we can match these scattering data very well.

Effect of wave function on the proton induced L XRP cross sections for {sub 62}Sm and {sub 74}W

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

Shehla,; Kaur, Rajnish; Kumar, Anil

The L{sub k}(k= 1, α, β, γ) X-ray production cross sections have been calculated for {sub 74}W and {sub 62}Sm at different incident proton energies ranging 1-5 MeV using theoretical data sets of different physical parameters, namely, the Li(i=1-3) sub-shell X-ray emission rates based on the Dirac-Fork (DF) model, the fluorescence and Coster Kronig yields based on the Dirac- Hartree-Slater (DHS) model and two sets the proton ionization cross sections based on the DHS model and the ECPSSR in order to assess the influence of the wave function on the XRP cross sections. The calculated cross sections have been compared withmore » the measured cross sections reported in the recent compilation to check the reliability of the calculated values.« less

Matching the laser wavelength to the absorption properties of matrices increases the ion yield in UV-MALDI mass spectrometry.

PubMed

Wiegelmann, Marcel; Soltwisch, Jens; Jaskolla, Thorsten W; Dreisewerd, Klaus

2013-09-01

A high analytical sensitivity in ultraviolet matrix-assisted laser desorption ionization mass spectrometry (MALDI-MS) is only achieved if the laser wavelength corresponds to a high optical absorption of the matrix. Laser fluence and the physicochemical properties of the compounds, e.g., the proton affinity, also influence analytical sensitivity significantly. In combination, these parameters determine the amount of material ejected per laser pulse and the ion yield, i.e., the fraction of ionized biomolecules. Here, we recorded peptide ion signal intensities as a function of these parameters. Three cinnamic acid matrices were investigated: α-cyano-4-hydroxycinnamic acid, α-cyano-4-chlorocinnamic acid, and α-cyano-2,4-difluorocinnamic acid. In addition, 2,5-dihydroxybenzoic acid was used in comparison experiments. Ion signal intensities "per laser shot" and integrated ion signal intensities were acquired over 900 consecutive laser pulses applied on distinct positions on the dried-droplet sample preparations. With respect to laser wavelength, the two standard MALDI wavelengths of 337/355 nm were investigated. Also, 305 or 320 nm was selected to account for the blue-shifted absorption profiles of the halogenated derivatives. Maximal peptide ion intensities were obtained if the laser wavelength fell within the peak of the absorption profile of the compound and for fluences two to three times the corresponding ion detection threshold. The results indicate ways for improving the analytical sensitivity in MALDI-MS, and in particular for MALDI-MS imaging applications where a limited amount of material is available per irradiated pixel.

Enhanced ionization efficiency in TIMS analyses of plutonium and americium using porous ion emitters

DOE PAGES

Baruzzini, Matthew L.; Hall, Howard L.; Watrous, Matthew G.; ...

2016-12-05

Investigations of enhanced sample utilization in thermal ionization mass spectrometry (TIMS) using porous ion emitter (PIE) techniques for the analyses of trace quantities of americium and plutonium were performed. Repeat ionization efficiency (i.e., the ratio of ions detected to atoms loaded on the filament) measurements were conducted on sample sizes ranging from 10–100 pg for americium and 1–100 pg for plutonium using PIE and traditional (i.e., a single, zone-refined rhenium, flat filament ribbon with a carbon ionization enhancer) TIMS filament sources. When compared to traditional filaments, PIEs exhibited an average boost in ionization efficiency of ~550% for plutonium and ~1100%more » for americium. A maximum average efficiency of 1.09% was observed at a 1 pg plutonium sample loading using PIEs. Supplementary trials were conducted using newly developed platinum PIEs to analyze 10 pg mass loadings of plutonium. As a result, platinum PIEs exhibited an additional ~134% boost in ion yield over standard PIEs and ~736% over traditional filaments at the same sample loading level.« less

Dissociation reactions of potassiated glucose: deionization, potassium hydroxide loss, and cross-ring dissociation

NASA Astrophysics Data System (ADS)

Dyakov, Y. A.; Kazaryan, M. A.; Golubkov, M. G.; Gubanova, D. P.; Asratyan, A. A.

2018-04-01

Photochemical properties of carbohydrates, including mono- and polysaccharides, as well as various kinds of glycoproteins, proteoglycans, and glycolipids, take great attention last decades due to their significance for clarifying physical and chemical processes happening in biological molecules under irradiation. Understanding of excitation and ionization processes is important for interpretation of mass spectrometric (MS) experiments, which is the main instrument for quick and reliable analysis of biological samples. While polynucleotides and simple proteins can be easily studied by standard MS techniques (MALDI, ESI, and CID), carbohydrates and complicated biomolecules containing oligosaccharide residues are difficult to be ionized. Carbohydrates give a low signal yield. Their detection and analysis requires the special equipment and technology. Therefore, the development of new efficient methods for identification of carbohydrates in biological samples currently is the critical scientific and technical problem. In this work we study dissociation processes taking place in potassiated α- and β-glucose, which can be concerned as the modelling molecule for investigation of wide range of carbohydrates and carbohydrate fragments of biomolecules containing potassium ion as the ionization source. Here we compare deionization process with H2O and KOH elimination channels, as far as their competition with cross-ring dissociation processes. Potential energy surface were optimized by the density functional B3LYP/6-31G* method. Single point energy calculations in minima and transition state points were performed by G3(MP2,CCSD) ab initio method.

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

Zhang, Shuai; Driver, Kevin P.; Soubiran, Francois

As one of the simple alkali metals, sodium has been of fundamental interest for shock physics experiments, but knowledge of its equation of state (EOS) in hot, dense regimes is not well known. By combining path integral Monte Carlo (PIMC) results for partially ionized states at high temperatures and density functional theory molecular dynamics (DFT-MD) results at lower temperatures, we have constructed a coherent equation of state for sodium over a wide density-temperature range of 1.93-11.60 g/cm 3 and 10 3–1.29×10 8 K. We find that a localized, Hartree-Fock nodal structure in PIMC yields pressures and internal energies that aremore » consistent with DFT-MD at intermediate temperatures of 2×10 6 K. Since PIMC and DFT-MD provide a first-principles treatment of electron shell and excitation effects, we are able to identify two compression maxima in the shock Hugoniot curve corresponding to K-shell and L-shell ionization. Our Hugoniot curves provide a benchmark for widely used EOS models: SESAME, LEOS, and Purgatorio. Due to the low ambient density, sodium has an unusually high first compression maximum along the shock Hugoniot curve. At beyond 10 7 K, we show that the radiation effect leads to very high compression along the Hugoniot curve, surpassing relativistic corrections, and observe an increasing deviation of the shock and particle velocities from a linear relation. Here, we also compute the temperature-density dependence of thermal and pressure ionization processes.« less

Comparison of different substrates for laser-induced electron transfer desorption/ionization of metal complexes

NASA Astrophysics Data System (ADS)

Grechnikov, A. A.; Georgieva, V. B.; Donkov, N.; Borodkov, A. S.; Pento, A. V.; Raicheva, Z. G.; Yordanov, Tc A.

2016-03-01

Four different substrates, namely, graphite, tungsten, amorphous silicon (α-Si) and titanium dioxide (TiO2) films, were compared in view of the laser-induced electron transfer desorption/ionization (LETDI) of metal coordination complexes. A rhenium complex with 8-mercaptoquinoline, a copper complex with diphenylthiocarbazone and chlorophyll A were studied as the test analytes. The dependencies of the ion yield and the surface temperature on the incident radiation fluence were investigated experimentally and theoretically. The temperature was estimated using the numerical solution of a one-dimensional heat conduction problem with a heat source distributed in time and space. It was found that at the same temperature, the ion yield from the different substrates varies in the range of three orders of magnitude. The direct comparison of all studied substrates revealed that LETDI from the TiO2 and α-Si films offer a better choice for producing molecular ions of metal coordination complexes.

Sample preparation for sequencing hits from one-bead-one-peptide combinatorial libraries by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry.

PubMed

Martínez-Ceron, María C; Giudicessi, Silvana L; Marani, Mariela M; Albericio, Fernando; Cascone, Osvaldo; Erra-Balsells, Rosa; Camperi, Silvia A

2010-05-15

Optimization of bead analysis by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS) after the screening of one-bead-one-peptide combinatorial libraries was achieved, involving the fine-tuning of the whole process. Guanidine was replaced by acetonitrile (MeCN)/acetic acid (AcOH)/water (H(2)O), improving matrix crystallization. Peptide-bead cleavage with NH(4)OH was cheaper and safer than, yet as efficient as, NH(3)/tetrahydrofuran (THF). Peptide elution in microtubes instead of placing the beads in the sample plate yielded more sample aliquots. Successive dry layers deposit sample preparation was better than the dried droplet method. Among the matrices analyzed, alpha-cyano-4-hydroxycinnamic acid resulted in the best peptide ion yield. Cluster formation was minimized by the addition of additives to the matrix. Copyright 2010 Elsevier Inc. All rights reserved.

Experimental and theoretical study of 2,6-difluorophenylnitrene, its radical cation, and their rearrangement products in argon matrices.

PubMed

Carra, Claudio; Nussbaum, Rafael; Bally, Thomas

2006-06-12

2,6-Difluorophenylnitrene was reinvestigated both experimentally, in Ar matrices at 10 K, and computationally, by DFT and CASSCF/CASPT2 calculations. Almost-pure samples of both neutral rearrangement products (the bicyclic azirine and the cyclic ketenimine) of a phenylnitrene were prepared and characterized for the first time. These samples were then subjected to X-irradiation in the presence of CH2Cl2 as an electron scavenger, which led to ionization of the neutral intermediates. Thereby, it was shown that only the phenylnitrene and the cyclic ketenimine yield stable radical cations, whereas the bicyclic azirine decays to both of these compounds on ionization. The cyclic ketenimine yields a novel aromatic azatropylium-type radical cation. The electronic structure of the title compound is discussed in detail, and its relation to those of the iso-pi-electronic benzyl radical and phenylcarbene is traced.

Chemical characterization of organic aerosol above a mid-latitude forest reveals a complex mixture of highly-functionalized chemical species and diverse structural features with temporal variability

NASA Astrophysics Data System (ADS)

Gentner, D. R.; Ditto, J.; Barnes, E.; Khare, P.

2017-12-01

Highly-functionalized organic compounds are known to be a major component of the complex mixture of the particle-phase compounds that comprise organic aerosol, yet little is known about the identity of many of these compounds, and their formation pathways and roles in atmospheric processes are poorly understood. We present results from the comprehensive chemical speciation of PM10 organic aerosols collected in July 2016 at the remote mid-latitude forest field site during PROPHET. Samples were analyzed via liquid and gas chromatography coupled with a quadrupole time-of-flight tandem mass spectrometry (MS×MS) following electrospray ionization (ESI) and atmospheric pressure chemical ionization (APCI). 8 hr samples were collected during day- and night-time sampling periods rather than more typical 24-hour samples. This analysis of the organic aerosol yielded over 12,000 unique compounds for which we have high accuracy molecular masses, formulas, and additional information on structural features using MS×MS. O:C ratios were 0.3 on average, yet the top 10% of compounds ranged 0.7-2.3. 70% and 69% of day- and night-time samples were nitrogen-containing, whereas 26% and 24% contained sulfur, respectively. Within these broader molecular categories, we observed a wide variety of molecular features that reveal a diversity of functional groups and moieties. In this presentation, we present the results of our speciation, temporal variability, connections to air parcel back trajectories and other bulk properties, and potential formation pathways.

Phase Transition to an Opaque Plasma in a Sonoluminescing Bubble

NASA Astrophysics Data System (ADS)

Kappus, Brian; Khalid, Shahzad; Chakravarty, Avik; Putterman, Seth

2011-06-01

Time-resolved spectrum measurements of a sonoluminescing Xe bubble reveal a transition from transparency to an opaque Planck blackbody. As the temperature is <10000K and the density is below liquid density, the photon scattering length is 10 000 times too large to explain its opacity. We resolve this issue with a model that reduces the ionization potential. According to this model, sonoluminescence originates in a new phase of matter with high ionization. Analysis of line emission from Xe* also yields evidence of phase segregation for this first-order transition inside a bubble.

Performance and cost analysis of matrix-assisted laser desorption ionization-time of flight mass spectrometry for routine identification of yeast.

PubMed

Dhiman, Neelam; Hall, Leslie; Wohlfiel, Sherri L; Buckwalter, Seanne P; Wengenack, Nancy L

2011-04-01

Matrix-assisted laser desorption ionization-time of flight (MALDI-TOF) mass spectrometry was compared to phenotypic testing for yeast identification. MALDI-TOF mass spectrometry yielded 96.3% and 84.5% accurate species level identifications (spectral scores, ≥ 1.8) for 138 common and 103 archived strains of yeast. MALDI-TOF mass spectrometry is accurate, rapid (5.1 min of hands-on time/identification), and cost-effective ($0.50/sample) for yeast identification in the clinical laboratory.

Barium release system

NASA Technical Reports Server (NTRS)

Lewis, B. W.; Stokes, C. S.; Smith, E. W.; Murphy, W. J. (Inventor)

1973-01-01

A chemical system is described for releasing a good yield of free barium neutral atoms and barium ions in the upper atmosphere and interplanetary space for the study of the geophysical properties of the medium. The barium is released in the vapor phase so that it can be ionized by solar radiation and also be excited to emit resonance radiation in the visible range. The ionized luminous cloud of barium becomes a visible indication of magnetic and electrical characteristics in space and allows determination of these properties over relatively large areas at a given time.

The role of partitioning of reagents in grafting and curing reactions initiated by ionizing radiation and UV

NASA Astrophysics Data System (ADS)

Chaplin, R. P.; Dworjanyn, P. A.; Gamage, N. J. W.; Garnett, J. L.; Jankiewicz, S. V.; Khan, M. A.; Sangster, D. F.

1996-03-01

Experimental evidence involving monomer absorption studies using tritiated styrene is shown to support the proposal that additives such as mineral acids and certain inorganic salts when dissolved in the monomer solution enhance radiation grafting yields by a mechanism involving partitioning of reagents. Photoinitiators such as benzoin ethyl ether and its methyl analogue are reported as new additives for grafting of styrene in methanol to cellulose and polypropylene initiated by ionizing radiation. The partitioning concept is shown to be relevant in analogous UV grafting and curing processes.

Effect of Initial Conditions on Gas-Puff Z-Pinch Dynamics.

NASA Astrophysics Data System (ADS)

Peterson, Gus Gordon

This dissertation concerns the effects initial conditions have on the dynamics of an imploded, annular gas-puff z-pinch. The influence of axial magnetic fields, nozzle size and composition, different gases, pre-ionization, and electrode design on pinch quality and x-ray yield is investigated. The experiment uses a 5-kJ capacitor bank to deliver 0.35 MA to the pinch load in 1.4 mu rm s. This research establishes parameters important to increasing the x-ray yield of dense z-pinches. The initial stage of the implosion is diagnosed with a framing camera that photographs visible light emitted from z-pinch gas breakdown. Data from subsequent stages of the pinch is recorded with a B-dot probe, filtered x-ray diodes, an x-ray filtered pinhole camera, and a nitrogen laser interferometer. Applied axial magnetic fields of ~100 gauss increase average x-ray yield by more than 20%. A substantial increase of K-shell x -ray yield of more than 200% was obtained by increasing the energy delivered to the plasma by enlarging the nozzle diameter from 4 to 5 cm. The use of a Teflon outer-mantle for the nozzle resulted in less uniform gas breakdown as compared to graphite and copper outer-mantles, but x-ray yield and final state uniformity were not reduced. Lower Z gases showed poorer breakdown uniformity. Pre-ionization improved the uniformity of helium and neon breakdown but did not appear to affect subsequent dynamics. X-ray yield was significantly higher using a knife-edge annular anode, as opposed to a flat stainless steel honeycomb anode. Annular anodes with diameters more than a few millimeters different than the nozzle diameter produced low quality pinches with substantially lower x-ray yield.

Quasar Outflows and AGN Feedback in the Extreme UV: HST/COS Observations of QSO HE0238-1904

NASA Astrophysics Data System (ADS)

Arav, Nahum; Borguet, B.; Chamberlain, C.; Edmonds, D.; Danforth, C.

2014-01-01

Spectroscopic observations of quasar outflows at rest-frame 500-1000 Angstrom have immense diagnostic power. We present analyses of such data, where absorption troughs from three important ions are measured: first, O IV and O IV* that allow us to obtain the distance of high ionization outflows from the AGN; second, Ne VIII and Mg X that are sensitive to the very high ionization phase of the outflow. Their inferred column densities, combined with those of troughs from O VI, N IV, and H I, yield two important results: 1) The outflow shows two ionization phases, where the high ionization phase carries the bulk of the material. This is similar to the situation seen in x-ray warm absorber studies. Furthermore, the low ionization phase is inferred to have a volume filling factor of 10^(-5)-10^(-6). 2) From the O IV to O IV* column density ratio, and the knowledge of the ionization parameter, we determine a distance of 3000 pc. from the outflow to the central source. Since this is a typical high ionization outflow, we can determine robust values for the mass flux and kinetic luminosity of the outflow: 40 solar masses per year and 10^45 ergs/s, respectively, where the latter is roughly equal to 1% of the bolometric luminosity. Such a large kinetic luminosity and mass flow rate measured in a typical high ionization wind suggests that quasar outflows are a major contributor to AGN feedback mechanisms.

The Au(n) cluster probe in secondary ion mass spectrometry: influence of the projectile size and energy on the desorption/ionization rate from biomolecular solids.

PubMed

Novikov, Alexey; Caroff, Martine; Della-Negra, Serge; Depauw, Joël; Fallavier, Mireille; Le Beyec, Yvon; Pautrat, Michèle; Schultz, J Albert; Tempez, Agnès; Woods, Amina S

2005-01-01

A Au-Si liquid metal ion source which produces Au(n) clusters over a large range of sizes was used to study the dependence of both the molecular ion desorption yield and the damage cross-section on the size (n = 1 to 400) and on the kinetic energy (E = 10 to 500 keV) of the clusters used to bombard bioorganic surfaces. Three pure peptides with molecular masses between 750 and 1200 Da were used without matrix. [M+H](+) and [M+cation](+) ion emission yields were enhanced by as much as three orders of magnitude when bombarding with Au(400) (4+) instead of monatomic Au(+), yet very little damage was induced in the samples. A 100-fold increase in the molecular ion yield was observed when the incident energy of Au(9) (+) was varied from 10 to 180 keV. Values of emission yields and damage cross-sections are presented as a function of cluster size and energy. The possibility to adjust both cluster size and energy, depending on the application, makes the analysis of biomolecules by secondary ion mass spectrometry an extremely powerful and flexible technique, particularly when combined with orthogonal time-of-flight mass spectrometry that then allows fast measurements using small primary ion beam currents. Copyright (c) 2005 John Wiley & Sons, Ltd.

Shock-wave structure in a partially ionized gas

NASA Technical Reports Server (NTRS)

Lu, C. S.; Huang, A. B.

1974-01-01

The structure of a steady plane shock in a partially ionized gas has been investigated using the Boltzmann equation with a kinetic model as the governing equation and the discrete ordinate method as a tool. The effects of the electric field induced by the charge separation on the shock structure have also been studied. Although the three species of an ionized gas travel with approximately the same macroscopic velocity, the individual distribution functions are found to be very different. In a strong shock the atom distribution function may have double peaks, while the ion distribution function has only one peak. Electrons are heated up much earlier than ions and atoms in a partially ionized gas. Because the interactions of electrons with atoms and with ions are different, the ion temperature can be different from the atom temperature.

Exclusion limits on the WIMP nucleon elastic scattering cross-section from the Cryogenic Dark Matter Search

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

Golwala, Sunil Ramanlal

2000-01-01

Extensive evidence indicates that a large fraction of the matter in the universe is nonluminous, nonbaryonic, and “cold” — nonrelativistic at the time matter began to dominate the energy density of the universe. Weakly Interacting Massive Particles (WIMPs) are an excellent candidate for nonbaryonic, cold dark matter. Minimal supersymmetry provides a natural WIMP candidate in the form of the lightest superpartner, with a typical mass Mδ ~ 100 GeV c-2 . WIMPs are expected to have collapsed into a roughly isothermal, spherical halo within which the visible portion of our galaxy resides. They would scatter off nuclei via the weakmore » interaction, potentially allowingtheir direct detection. The Cryogenic Dark Matter Search (CDMS) employs Ge and Si detectors to search for WIMPs via their elastic-scatteringinteractions with nuclei while discriminatingagainst interactions of background particles. The former yield nuclear recoils while the latter produce electron recoils. The ionization yield (the ratio of ionization production to recoil energy in a semiconductor) of a particle interaction differs greatly for nuclear and electron recoils. CDMS detectors measure phonon and electron-hole-pair production to determine recoil energy and ionization yield for each event and thereby discriminate nuclear recoils from electron recoils. This dissertation reports new limits on the spin-independent WIMP-nucleon elastic-scattering cross section that exclude unexplored parameter space above 10 GeV c-2 WIMP mass and, at > 75% CL, the entire 3σ allowed region for the WIMP signal reported by the DAMA experiment. The experimental apparatus, detector performance, and data analysis are fully described.« less

Connecting the dots: a correlation between ionizing radiation and cloud mass-loss rate traced by optical integral field spectroscopy

NASA Astrophysics Data System (ADS)

McLeod, A. F.; Gritschneder, M.; Dale, J. E.; Ginsburg, A.; Klaassen, P. D.; Mottram, J. C.; Preibisch, T.; Ramsay, S.; Reiter, M.; Testi, L.

2016-11-01

We present an analysis of the effect of feedback from O- and B-type stars with data from the integral field spectrograph Multi Unit Spectroscopic Explorer (MUSE) mounted on the Very Large Telescope of pillar-like structures in the Carina Nebular Complex, one of the most massive star-forming regions in the Galaxy. For the observed pillars, we compute gas electron densities and temperatures maps, produce integrated line and velocity maps of the ionized gas, study the ionization fronts at the pillar tips, analyse the properties of the single regions, and detect two ionized jets originating from two distinct pillar tips. For each pillar tip, we determine the incident ionizing photon flux Q0, pil originating from the nearby massive O- and B-type stars and compute the mass-loss rate dot{M} of the pillar tips due to photoevaporation caused by the incident ionizing radiation. We combine the results of the Carina data set with archival MUSE data of a pillar in NGC 3603 and with previously published MUSE data of the Pillars of Creation in M16, and with a total of 10 analysed pillars, find tight correlations between the ionizing photon flux and the electron density, the electron density and the distance from the ionizing sources, and the ionizing photon flux and the mass-loss rate. The combined MUSE data sets of pillars in regions with different physical conditions and stellar content therefore yield an empirical quantification of the feedback effects of ionizing radiation. In agreement with models, we find that dot{M}∝ Q_0,pil^{1/2}.

Comment on "Continuum Lowering and Fermi-Surface Rising in Stromgly Coupled and Degenerate Plasmas"

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

Iglesias, C. A.; Sterne, P. A.

In a recent Letter, Hu [1] reported photon absorption cross sections in strongly coupled, degenerate plasmas from quantum molecular dynamics (QMD). The Letter claims that the K-edge shift as a function of plasma density computed with simple ionization potential depression (IPD) models are in violent disagreement with the QMD results. The QMD calculations displayed an increase in Kedge shift with increasing density while the simpler models yielded a decrease. Here, this Comment shows that the claimed large errors reported by Hu for the widely used Stewart- Pyatt (SP) model [2] stem from an invalid comparison of disparate physical quantities andmore » is largely resolved by including well-known corrections for degenerate systems.« less

Analytical model for release calculations in solid thin-foils ISOL targets

NASA Astrophysics Data System (ADS)

Egoriti, L.; Boeckx, S.; Ghys, L.; Houngbo, D.; Popescu, L.

2016-10-01

A detailed analytical model has been developed to simulate isotope-release curves from thin-foils ISOL targets. It involves the separate modeling of diffusion and effusion inside the target. The former has been modeled using both first and second Fick's law. The latter, effusion from the surface of the target material to the end of the ionizer, was simulated with the Monte Carlo code MolFlow+. The calculated delay-time distribution for this process was then fitted using a double-exponential function. The release curve obtained from the convolution of diffusion and effusion shows good agreement with experimental data from two different target geometries used at ISOLDE. Moreover, the experimental yields are well reproduced when combining the release fraction with calculated in-target production.

Investigating the Fundamentals of Molecular Depth Profiling Using Strong-field Photoionization of Sputtered Neutrals

PubMed Central

Willingham, D.; Brenes, D. A.; Winograd, N.; Wucher, A.

2010-01-01

Molecular depth profiles of model organic thin films were performed using a 40 keV C60+ cluster ion source in concert with TOF-SIMS. Strong-field photoionization of intact neutral molecules sputtered by 40 keV C60+ primary ions was used to analyze changes in the chemical environment of the guanine thin films as a function of ion fluence. Direct comparison of the secondary ion and neutral components of the molecular depth profiles yields valuable information about chemical damage accumulation as well as changes in the molecular ionization probability. An analytical protocol based on the erosion dynamics model is developed and evaluated using guanine and trehalose molecular secondary ion signals with and without comparable laser photoionization data. PMID:26269660

Comment on "Continuum Lowering and Fermi-Surface Rising in Stromgly Coupled and Degenerate Plasmas"

DOE PAGES

Iglesias, C. A.; Sterne, P. A.

2018-03-16

In a recent Letter, Hu [1] reported photon absorption cross sections in strongly coupled, degenerate plasmas from quantum molecular dynamics (QMD). The Letter claims that the K-edge shift as a function of plasma density computed with simple ionization potential depression (IPD) models are in violent disagreement with the QMD results. The QMD calculations displayed an increase in Kedge shift with increasing density while the simpler models yielded a decrease. Here, this Comment shows that the claimed large errors reported by Hu for the widely used Stewart- Pyatt (SP) model [2] stem from an invalid comparison of disparate physical quantities andmore » is largely resolved by including well-known corrections for degenerate systems.« less

Slow Photoelectron Spectroscopy and State-Selected Unimolecular Decomposition of Ionized DNA Bases Analogues

NASA Astrophysics Data System (ADS)

Mahjoub, Ahmed; Hochlaf, Majdi; Poisson, Lionel; Garcia, Gustavo A.; Nahon, Laurent

2013-06-01

We studied the single-photon ionization of gas-phase 2-Piperidone (DNA basis analogue) and of its dimer using vacuum-ultraviolet (VUV) synchrotron radiation coupled to a velocity map imaging electron/ion coincidence spectrometer The slow photoelectron spectrum (SPES) of the monomer is dominated by the vibrational transitions to the ground state. These spectra are assigned with the help of theoretical calculations dealing with the equilibrium geometries, electronic-state patterns and evolutions, harmonic and anharmonic wavenumbers. After its formation, dimer is subject of intramolecular isomerization, H transfer and then unimolecular fragmentation processes. The near threshold photofragmentation pattern of the cationic 2-Piperidone cation and its dimer has been recorded. The experimental method yields the fragment intensity as a function of the internal energy deposited into the parent cation. In parallel, ab initio studies on ionic and neutral fragmentation products have been performed with the aim of determining the isomers of the ionic products observed experimentally as well as of their neutral counterparts. L. Nahon, N. De Oliveria,J. F. Gil,B. Pilette,O. Marcouillé, B. La garde and F. Polack Journal of Synchrotron Radiation {19}(4), 508-520; 2012

Monitoring Enzymatic Reactions in Real Time Using Venturi Easy Ambient Sonic-Spray Ionization Mass Spectrometry

PubMed Central

2016-01-01

We developed a technique to monitor spatially confined surface reactions with mass spectrometry under ambient conditions, without the need for voltage or organic solvents. Fused-silica capillaries immersed in an aqueous solution, positioned in close proximity to each other and the functionalized surface, created a laminar flow junction with a resulting reaction volume of ∼5 pL. The setup was operated with a syringe pump, delivering reagents to the surface through a fused-silica capillary. The other fused-silica capillary was connected to a Venturi easy ambient sonic-spray ionization source, sampling the resulting analytes at a slightly higher flow rate compared to the feeding capillary. The combined effects of the inflow and outflow maintains a chemical microenvironment, where the rate of advective transport overcomes diffusion. We show proof-of-concept where acetylcholinesterase was immobilized on an organosiloxane polymer through electrostatic interactions. The hydrolysis of acetylcholine by acetylcholinesterase into choline was monitored in real-time for a range of acetylcholine concentrations, fused-silica capillary geometries, and operating flow rates. Higher reaction rates and conversion yields were observed with increasing acetylcholine concentrations, as would be expected. PMID:27249533

Derivatized graphitic nanofibres (GNF) as a new support material for mass spectrometric analysis of peptides and proteins.

PubMed

Greiderer, Andreas; Rainer, Matthias; Najam-ul-Haq, Muhammad; Vallant, Rainer M; Huck, Christian W; Bonn, Günther K

2009-07-01

Graphitic nanofibres (GNFs), 100-200 nm in diameter and 5-20 microm in length have been modified in order to yield different affinities (Cu2+ and Fe3+ loaded immobilized metal affinity chromatography (IMAC) as well as cation and anion exchange materials) for the extraction of a range of biomolecules by their inherited hydrophobicity and the hydrophilic chemical functionalities, obtained by derivatization. Modified GNFs have for the first time been employed as carrier materials for protein profiling in material-enhanced laser desorption/ionization (MELDI) for the enrichment and screening of biofluids. For that purpose, the derivatized GNF materials have comprehensively been characterized regarding surface area, structural changes during derivatization, IMAC, as well as ion exchange and protein-loading capacity and recovery. GNF derivatives revealed high protein-binding capacity (2,000 microg ml(-1) for insulin) and ideal sensitivities, resulting in a detection limit of 50 fmol microl(-1) (for insulin), which is crucial for the detection of low abundant species in biological samples. Compared to other MELDI carrier materials, sensitivity was enhanced on GNF derivatives, which might be ascribed to the fact that GNFs support desorption and ionization mechanisms and by absorbing laser energy in addition to matrix.

Photochemical Degradation of Composition B and Its Components

DTIC Science & Technology

2007-09-01

recorded on the toluene (5.7 mg yield ), ether I (35 mg), and aceto- nitrile (17.8 mg) fractions. Irradiation of solution explosives in soils A...the soil was Soxhlet extracted with acetonitrile for 93 hours. The acetonitrile was removed with a rotary evaporator and the residue redissolved in...ionization to yield an anion of m/z 226. The traces show differences observed in samples with different initial preparation protocols at 15 days. Distance

Optimizing the ionization and energy absorption of laser-irradiated clusters

NASA Astrophysics Data System (ADS)

Kundu, M.; Bauer, D.

2008-03-01

It is known that rare-gas or metal clusters absorb incident laser energy very efficiently. However, due to the intricate dependencies on all the laser and cluster parameters, it is difficult to predict under which circumstances ionization and energy absorption are optimal. With the help of three-dimensional particle-in-cell simulations of xenon clusters (up to 17256 atoms), it is shown that for a given laser pulse energy and cluster, an optimum wavelength exists that corresponds to the approximate wavelength of the transient, linear Mie-resonance of the ionizing cluster at an early stage of negligible expansion. In a single ultrashort laser pulse, the linear resonance at this optimum wavelength yields much higher absorption efficiency than in the conventional, dual-pulse pump-probe setup of linear resonance during cluster expansion.

Tunneling ionization and harmonic generation in two-color fields

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

Kondo, K.; Kobayashi, Y.; Sagisaka, A.

1996-02-01

Tunneling ionization and harmonic generation in two-color fields were studied with a fundamental beam ({omega}) and its harmonics (2{omega},3{omega}), which were generated by a 100-fs Ti:sapphire laser. Ion yields of atoms and molecules were successfully controlled by means of a change in the relative phase between {omega} and 3{omega} pulses. Two-color interference was clearly observed in photoelectron spectra and harmonic spectra. In the {omega}{endash}2{omega} field even-order harmonics were observed in which the intensity was almost equal to that of the odd harmonics because of an asymmetric optical field. These results were compared with the quasi-static model for ionization and withmore » the quantum theory for harmonic generation. {copyright} {ital 1996 Optical Society of America.}« less

Single-shot carrier-envelope-phase-tagged ion-momentum imaging of nonsequential double ionization of argon in intense 4-fs laser fields

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

Johnson, Nora G.; Herrwerth, O.; Wirth, A.

2011-01-15

Single-shot carrier-envelope-phase (CEP) tagging is combined with a reaction mircoscope (REMI) to investigate CEP-dependent processes in atoms. Excellent experimental stability and data acquisition longevity are achieved. Using this approach, we study the CEP effects for nonsequential double ionization of argon in 4-fs laser fields at 750 nm and an intensity of 1.6x10{sup 14} W/cm{sup 2}. The Ar{sup 2+} ionization yield shows a pronounced CEP dependence which compares well with recent theoretical predictions employing quantitative rescattering theory [S. Micheau et al., Phys. Rev. A 79, 013417 (2009)]. Furthermore, we find strong CEP influences on the Ar{sup 2+} momentum spectra along themore » laser polarization axis.« less

In-Line Detection and Measurement of Molecular Contamination in Semiconductor Process Solutions

NASA Astrophysics Data System (ADS)

Wang, Jason; West, Michael; Han, Ye; McDonald, Robert C.; Yang, Wenjing; Ormond, Bob; Saini, Harmesh

2005-09-01

This paper discusses a fully automated metrology tool for detection and quantitative measurement of contamination, including cationic, anionic, metallic, organic, and molecular species present in semiconductor process solutions. The instrument is based on an electrospray ionization time-of-flight mass spectrometer (ESI-TOF/MS) platform. The tool can be used in diagnostic or analytical modes to understand process problems in addition to enabling routine metrology functions. Metrology functions include in-line contamination measurement with near real-time trend analysis. This paper discusses representative organic and molecular contamination measurement results in production process problem solving efforts. The examples include the analysis and identification of organic compounds in SC-1 pre-gate clean solution; urea, NMP (N-Methyl-2-pyrrolidone) and phosphoric acid contamination in UPW; and plasticizer and an organic sulfur-containing compound found in isopropyl alcohol (IPA). It is expected that these unique analytical and metrology capabilities will improve the understanding of the effect of organic and molecular contamination on device performance and yield. This will permit the development of quantitative correlations between contamination levels and process degradation. It is also expected that the ability to perform routine process chemistry metrology will lead to corresponding improvements in manufacturing process control and yield, the ability to avoid excursions and will improve the overall cost effectiveness of the semiconductor manufacturing process.

Pyroelectricity Assisted Infrared-Laser Desorption Ionization (PAI-LDI) for Atmospheric Pressure Mass Spectrometry

NASA Astrophysics Data System (ADS)

Li, Yanyan; Ma, Xiaoxiao; Wei, Zhenwei; Gong, Xiaoyun; Yang, Chengdui; Zhang, Sichun; Zhang, Xinrong

2015-08-01

A new atmospheric pressure ionization method termed pyroelectricity-assisted infrared laser desorption ionization (PAI-LDI) was developed in this study. The pyroelectric material served as both sample target plate and enhancing ionization substrate, and an IR laser with wavelength of 1064 nm was employed to realize direct desorption and ionization of the analytes. The mass spectra of various compounds obtained on pyroelectric material were compared with those of other substrates. For the five standard substances tested in this work, LiNbO3 substrate produced the highest ion yield and the signal intensity was about 10 times higher than that when copper was used as substrate. For 1-adamantylamine, as low as 20 pg (132.2 fmol) was successfully detected. The active ingredient in (Compound Paracetamol and 1-Adamantylamine Hydrochloride Capsules), 1-adamantylamine, can be sensitively detected at an amount as low as 150 pg, when the medicine stock solution was diluted with urine. Monosaccharide and oligosaccharides in Allium Cepa L. juice was also successfully identified with PAI-LDI. The method did not require matrix-assisted external high voltage or other extra facility-assisted set-ups for desorption/ionization. This study suggested exciting application prospect of pyroelectric materials in matrix- and electricity-free atmospheric pressure mass spectrometry research.

Detection of explosives using negative ion mobility spectrometry in air based on dopant-assisted thermal ionization.

PubMed

Shahraki, Hassan; Tabrizchi, Mahmoud; Farrokhpor, Hossein

2018-05-26

The ionization source is an essential component of most explosive detectors based on negative ion mobility spectrometry. Conventional ion sources suffer from such inherent limitations as special safety regulations on radioactive sources or generating interfering ions (for non-radioactive sources) such as corona discharge operating in the air. In this study, a new negative ion source is introduced for ion mobility spectrometry that is based on thermal ionization and operates in the air, applicable to explosives detection. Our system consists of a heating filament powered by an isolated power supply connected to negative high voltage. The ionization is assisted by doping chlorinated compounds in the gas phase using chlorinated hydrocarbons in contact with the heating element to yield Cl - reactant ions. Several chlorinated hydrocarbons are evaluated as the reagent chemicals for providing Cl- reactant ions, of which CCl 4 is identified as the best ionizing reagent. The ion source is evaluated by recording the ion mobility spectra of common explosives, including TNT, RDX, and PETN in the air. A detection limit of 150 pg is obtained for TNT. Compared to other ionization sources, the new source is found to be low-cost, simple, and long-lived, making it suited to portable explosives detection devices. Copyright © 2018 Elsevier B.V. All rights reserved.

Directed Field Ionization: A Genetic Algorithm for Evolving Electric Field Pulses

NASA Astrophysics Data System (ADS)

Kang, Xinyue; Rowley, Zoe A.; Carroll, Thomas J.; Noel, Michael W.

2017-04-01

When an ionizing electric field pulse is applied to a Rydberg atom, the electron's amplitude traverses many avoided crossings among the Stark levels as the field increases. The resulting superposition determines the shape of the time resolved field ionization spectrum at a detector. An engineered electric field pulse that sweeps back and forth through avoided crossings can control the phase evolution so as to determine the electron's path through the Stark map. In the region of n = 35 in rubidium there are hundreds of potential avoided crossings; this yields a large space of possible pulses. We use a genetic algorithm to search this space and evolve electric field pulses to direct the ionization of the Rydberg electron in rubidium. We present the algorithm along with a comparison of simulated and experimental results. This work was supported by the National Science Foundation under Grants No. 1607335 and No. 1607377 and used the Extreme Science and Engineering Discovery Environment (XSEDE), which is supported by National Science Foundation Grant Number OCI-1053575.

Ionization Chemistry and Role of Grains on Non-ideal MHD Effects in Protoplanetary Disks

NASA Astrophysics Data System (ADS)

Xu, Rui; Bai, Xue-Ning; Oberg, Karin I.

2015-01-01

Ionization in protoplanetary disks (PPDs) is one of the key elements for understanding disk chemistry. It also determines the coupling between gas and magnetic fields hence strongly affect PPD gas dynamics. We study the ionization chemistry in the presence of grains in the midplane region of PPDs and its impact on gas conductivity reflected in non-ideal MHD effects including Ohmic resistivity, Hall effect and ambipolar diffusion. We first develop a reduced chemical reaction network from the UMIST database. The reduced network contains much smaller number of species and reactions while yields reliable estimates of the disk ionization level compared with the full network. We further show that grains are likely the dominant charge carrier in the midplane regions of the inner disk, which significantly affects the gas conductivity. In particular, ambipolar diffusion is strongly reduced and the Hall coefficient changes sign in the presence of strong magnetic field. The latter provides a natural mechanism to the saturation of the Hall-shear instability.

Establishment of a Charge Reversal Derivatization Strategy to Improve the Ionization Efficiency of Limaprost and Investigation of the Fragmentation Patterns of Limaprost Derivatives Via Exclusive Neutral Loss and Survival Yield Method

NASA Astrophysics Data System (ADS)

Sun, Dong; Meng, Xiangjun; Ren, Tianming; Fawcett, John Paul; Wang, Hualu; Gu, Jingkai

2018-04-01

Sensitivity is generally an issue in bioassays of prostaglandins and their synthetic analogs due to their extremely low concentration in vivo. To improve the ionization efficiency of limaprost, an oral prostaglandin E1 (PGE1) synthetic analog, we investigated a charge reversal derivatization strategy in electrospray ionization mass spectrometry (ESI-MS). We established that the cholamine derivative exhibits much greater signal intensity in the positive-ion mode compared with limaprost in the negative ion mode. Collision-induced dissociation (CID) involved exclusive neutral mass loss and positive charge migration to form stable cationic product ions with the positive charge on the limaprost residue rather than on the modifying group. This has the effect of maintaining the efficiency and specificity of multiple reaction monitoring (MRM) and avoiding cross talk. CID fragmentation patterns of other limaprost derivatives allowed us to relate the dissociation tendency of different neutral leaving groups to an internal energy distribution scale based on the survival yield method. Knowledge of the energy involved in the production of stabilized positive ions will potentially assist the selection of suitable derivatization reagents for the analysis of a wide variety of lipid acids. [Figure not available: see fulltext.

Real Time Monitoring of Containerless Microreactions in Acoustically Levitated Droplets via Ambient Ionization Mass Spectrometry.

PubMed

Crawford, Elizabeth A; Esen, Cemal; Volmer, Dietrich A

2016-09-06

Direct in-droplet (in stillo) microreaction monitoring using acoustically levitated micro droplets has been achieved by combining acoustic (ultrasonic) levitation for the first time with real time ambient tandem mass spectrometry (MS/MS). The acoustic levitation and inherent mixing of microliter volumes of reactants (3 μL droplets), yielding total reaction volumes of 6 μL, supported monitoring the acid-catalyzed degradation reaction of erythromycin A. This reaction was chosen to demonstrate the proof-of-principle of directly monitoring in stillo microreactions via hyphenated acoustic levitation and ambient ionization mass spectrometry. The microreactions took place completely in stillo over 30, 60, and 120 s within the containerless stable central pressure node of an acoustic levitator, thus readily promoting reaction miniaturization. For the evaluation of the miniaturized in stillo reactions, the degradation reactions were also carried out in vials (in vitro) with a total reaction volume of 400 μL. The reacted in vitro mixtures (6 μL total) were similarly introduced into the acoustic levitator prior to ambient ionization MS/MS analysis. The in stillo miniaturized reactions provided immediate real-time snap-shots of the degradation process for more accurate reaction monitoring and used a fraction of the reactants, while the larger scale in vitro reactions only yielded general reaction information.

Increasing the applicability of density functional theory. V. X-ray absorption spectra with ionization potential corrected exchange and correlation potentials.

PubMed

Verma, Prakash; Bartlett, Rodney J

2016-07-21

Core excitation energies are computed with time-dependent density functional theory (TD-DFT) using the ionization energy corrected exchange and correlation potential QTP(0,0). QTP(0,0) provides C, N, and O K-edge spectra to about an electron volt. A mean absolute error (MAE) of 0.77 and a maximum error of 2.6 eV is observed for QTP(0,0) for many small molecules. TD-DFT based on QTP (0,0) is then used to describe the core-excitation spectra of the 22 amino acids. TD-DFT with conventional functionals greatly underestimates core excitation energies, largely due to the significant error in the Kohn-Sham occupied eigenvalues. To the contrary, the ionization energy corrected potential, QTP(0,0), provides excellent approximations (MAE of 0.53 eV) for core ionization energies as eigenvalues of the Kohn-Sham equations. As a consequence, core excitation energies are accurately described with QTP(0,0), as are the core ionization energies important in X-ray photoionization spectra or electron spectroscopy for chemical analysis.

MASS SPECTROMETRY OF INDIVIDUAL AEROSOL PARTICLES. (R823980)

EPA Science Inventory

Typically, in real-time aerosol mass spectrometry (RTAMS), individual airborne particles
are ablated and ionized with a single focused laser pulse. This technique yields information that
permits bulk characterization of the particle, but information about the particle's sur...

Influence of renormalization shielding on the electron-impact ionization process in dense partially ionized plasmas

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

Song, Mi-Young; Yoon, Jung-Sik; Jung, Young-Dae, E-mail: ydjung@hanyang.ac.kr

2015-04-15

The renormalization shielding effects on the electron-impact ionization of hydrogen atom are investigated in dense partially ionized plasmas. The effective projectile-target interaction Hamiltonian and the semiclassical trajectory method are employed to obtain the transition amplitude as well as the ionization probability as functions of the impact parameter, the collision energy, and the renormalization parameter. It is found that the renormalization shielding effect suppresses the transition amplitude for the electron-impact ionization process in dense partially ionized plasmas. It is also found that the renormalization effect suppresses the differential ionization cross section in the peak impact parameter region. In addition, it ismore » found that the influence of renormalization shielding on the ionization cross section decreases with an increase of the relative collision energy. The variations of the renormalization shielding effects on the electron-impact ionization cross section are also discussed.« less

Electron impact fragmentation of thymine: partial ionization cross sections for positive fragments

NASA Astrophysics Data System (ADS)

van der Burgt, Peter J. M.; Mahon, Francis; Barrett, Gerard; Gradziel, Marcin L.

2014-06-01

We have measured mass spectra for positive ions for low-energy electron impact on thymine using a reflectron time-of-flight mass spectrometer. Using computer controlled data acquisition, mass spectra have been acquired for electron impact energies up to 100 eV in steps of 0.5 eV. Ion yield curves for most of the fragment ions have been determined by fitting groups of adjacent peaks in the mass spectra with sequences of normalized Gaussians. The ion yield curves have been normalized by comparing the sum of the ion yields to the average of calculated total ionization cross sections. Appearance energies have been determined. The nearly equal appearance energies of 83 u and 55 u observed in the present work strongly indicate that near threshold the 55 u ion is formed directly by the breakage of two bonds in the ring, rather than from a successive loss of HNCO and CO from the parent ion. Likewise 54 u is not formed by CO loss from 82 u. The appearance energies are in a number of cases consistent with the loss of one or more hydrogen atoms from a heavier fragment, but 70 u is not formed by hydrogen loss from 71 u.

Rapid Characterization of Microalgae and Microalgae Mixtures Using Matrix-Assisted Laser Desorption Ionization Time-Of-Flight Mass Spectrometry (MALDI-TOF MS)

PubMed Central

Barbano, Duane; Diaz, Regina; Zhang, Lin; Sandrin, Todd; Gerken, Henri; Dempster, Thomas

2015-01-01

Current molecular methods to characterize microalgae are time-intensive and expensive. Matrix Assisted Laser Desorption/Ionization Time-of-Flight Mass Spectrometry (MALDI-TOF MS) may represent a rapid and economical alternative approach. The objectives of this study were to determine whether MALDI-TOF MS can be used to: 1) differentiate microalgae at the species and strain levels and 2) characterize simple microalgal mixtures. A common protein extraction sample preparation method was used to facilitate rapid mass spectrometry-based analysis of 31 microalgae. Each yielded spectra containing between 6 and 56 peaks in the m/z 2,000 to 20,000 range. The taxonomic resolution of this approach appeared higher than that of 18S rDNA sequence analysis. For example, two strains of Scenedesmus acutus differed only by two 18S rDNA nucleotides, but yielded distinct MALDI-TOF mass spectra. Mixtures of two and three microalgae yielded relatively complex spectra that contained peaks associated with members of each mixture. Interestingly, though, mixture-specific peaks were observed at m/z 11,048 and 11,230. Our results suggest that MALDI-TOF MS affords rapid characterization of individual microalgae and simple microalgal mixtures. PMID:26271045

Assessment of Real-Time Time-Dependent Density Functional Theory (RT-TDDFT) in Radiation Chemistry: Ionized Water Dimer.

PubMed

Chalabala, Jan; Uhlig, Frank; Slavíček, Petr

2018-03-29

Ionization in the condensed phase and molecular clusters leads to a complicated chain of processes with coupled electron-nuclear dynamics. It is difficult to describe such dynamics with conventional nonadiabatic molecular dynamics schemes since the number of states swiftly increases as the molecular system grows. It is therefore attractive to use a direct electron and nuclear propagation such as the real-time time-dependent density functional theory (RT-TDDFT). Here we report a RT-TDDFT benchmark study on simulations of singly and doubly ionized states of a water monomer and dimer as a prototype for more complex processes in a condensed phase. We employed the RT-TDDFT based Ehrenfest molecular dynamics with a generalized gradient approximate (GGA) functional and compared it with wave-function-based surface hopping (SH) simulations. We found that the initial dynamics of a singly HOMO ionized water dimer is similar for both the RT-TDDFT/GGA and the SH simulations but leads to completely different reaction channels on a longer time scale. This failure is attributed to the self-interaction error in the GGA functionals and it can be avoided by using hybrid functionals with large fraction of exact exchange (represented here by the BHandHLYP functional). The simulations of doubly ionized states are reasonably described already at the GGA level. This suggests that the RT-TDDFT/GGA method could describe processes following the autoionization processes such as Auger emission, while its applicability to more complex processes such as intermolecular Coulombic decay remains limited.

LTC1877 High Efficiency Regulator Total Ionizing Dose Test Report

NASA Technical Reports Server (NTRS)

Oldham, Timothy; Pellish, Jonathan; Boutte, Alvin

2012-01-01

This report presents total ionizing dose evaluation data for the Linear Technology Corporation LTC1877 high efficiency monolithic synchronous step-down regulator. Data sheet parameters were tracked as a function of ionizing dose up to a total of 20 krad(SiO2). Control devices were also used.

Application of high-resolution time-of-flight chemical ionization mass spectrometry measurements to estimate volatility distributions of α-pinene and naphthalene oxidation products

DOE PAGES

Chhabra, P. S.; Lambe, A. T.; Canagaratna, M. R.; ...

2015-01-05

Recent developments in high-resolution time-of-flight chemical ionization mass spectrometry (HR-ToF-CIMS) have made it possible to directly detect atmospheric organic compounds in real time with high sensitivity and with little or no fragmentation, including low-volatility, highly oxygenated organic vapors that are precursors to secondary organic aerosol formation. Here, using ions identified by high-resolution spectra from an HR-ToF-CIMS with acetate reagent ion chemistry, we develop an algorithm to estimate the vapor pressures of measured organic acids. The algorithm uses identified ion formulas and calculated double bond equivalencies, information unavailable in quadrupole CIMS technology, as constraints for the number of possible oxygen-containing functionalmore » groups. The algorithm is tested with acetate chemical ionization mass spectrometry (acetate-CIMS) spectra of O 3 and OH oxidation products of α-pinene and naphthalene formed in a flow reactor with integrated OH exposures ranged from 1.2 × 10 11 to 9.7 × 10 11 molec s cm −3, corresponding to approximately 1.0 to 7.5 days of equivalent atmospheric oxidation. Measured gas-phase organic acids are similar to those previously observed in environmental chamber studies. For both precursors, we find that acetate-CIMS spectra capture both functionalization (oxygen addition) and fragmentation (carbon loss) as a function of OH exposure. The level of fragmentation is observed to increase with increased oxidation. The predicted condensed-phase secondary organic aerosol (SOA) average acid yields and O/C and H/C ratios agree within uncertainties with previous chamber and flow reactor measurements and ambient CIMS results. Furthermore, while acetate reagent ion chemistry is used to selectively measure organic acids, in principle this method can be applied to additional reagent ion chemistries depending on the application.« less

Mass Yields and Average Total Kinetic Energy Release in Fission for 235U, 238U, and 239Pu

NASA Astrophysics Data System (ADS)

Duke, Dana

2015-10-01

Mass yield distributions and average total kinetic energy (TKE) in neutron induced fission of 235U, 238U, and 239Pu targets were measured with a gridded ionization chamber. Despite decades of fission research, our understanding of how fragment mass yields and TKE depend on incident neutron energy is limited, especially at higher energies (above 5-10 MeV). Improved accuracy in these quantities is important for nuclear technology as it enhances our simulation capabilities and increases the confidence in diagnostic tools. The data can also guide and validate theoretical fission models where the correlation between the fragment mass and TKE is of particular value for constraining models. The Los Alamos Neutron Science Center - Weapons Neutron Research (LANSCE - WNR) provides a neutron beam with energies from thermal to hundreds of MeV, well-suited for filling in the gaps in existing data and exploring fission behavior in the fast neutron region. The results of the studies on target nuclei 235U, 238U, and 239Pu will be presented with a focus on exploring data trends as a function of neutron energy from thermal through 30 MeV. Results indicate clear evidence of structure due to multi-chance fission in the TKE . LA-UR-15-24761.

The Pillars of Creation revisited with MUSE: gas kinematics and high-mass stellar feedback traced by optical spectroscopy

NASA Astrophysics Data System (ADS)

McLeod, A. F.; Dale, J. E.; Ginsburg, A.; Ercolano, B.; Gritschneder, M.; Ramsay, S.; Testi, L.

2015-06-01

Integral field unit (IFU) data of the iconic Pillars of Creation in M16 are presented. The ionization structure of the pillars was studied in great detail over almost the entire visible wavelength range, and maps of the relevant physical parameters, e.g. extinction, electron density, electron temperature, line-of-sight velocity of the ionized and neutral gas are shown. In agreement with previous authors, we find that the pillar tips are being ionized and photoevaporated by the massive members of the nearby cluster NGC 6611. They display a stratified ionization structure where the emission lines peak in a descending order according to their ionization energies. The IFU data allowed us to analyse the kinematics of the photoevaporative flow in terms of the stratified ionization structure, and we find that, in agreement with simulations, the photoevaporative flow is traced by a blueshift in the position-velocity profile. The gas kinematics and ionization structure have allowed us to produce a sketch of the 3D geometry of the Pillars, positioning the pillars with respect to the ionizing cluster stars. We use a novel method to detect a previously unknown bipolar outflow at the tip of the middle pillar and suggest that it has an embedded protostar as its driving source. Furthermore we identify a candidate outflow in the leftmost pillar. With the derived physical parameters and ionic abundances, we estimate a mass-loss rate due to the photoevaporative flow of 70 M⊙ Myr-1 which yields an expected lifetime of approximately 3 Myr.

On-top density functionals for the short-range dynamic correlation between electrons of opposite and parallel spin

NASA Astrophysics Data System (ADS)

Hollett, Joshua W.; Pegoretti, Nicholas

2018-04-01

Separate, one-parameter, on-top density functionals are derived for the short-range dynamic correlation between opposite and parallel-spin electrons, in which the electron-electron cusp is represented by an exponential function. The combination of both functionals is referred to as the Opposite-spin exponential-cusp and Fermi-hole correction (OF) functional. The two parameters of the OF functional are set by fitting the ionization energies and electron affinities, of the atoms He to Ar, predicted by ROHF in combination with the OF functional to the experimental values. For ionization energies, the overall performance of ROHF-OF is better than completely renormalized coupled-cluster [CR-CC(2,3)] and better than, or as good as, conventional density functional methods. For electron affinities, the overall performance of ROHF-OF is less impressive. However, for both ionization energies and electron affinities of third row atoms, the mean absolute error of ROHF-OF is only 3 kJ mol-1.

Mass spectrometry of rhenium complexes: a comparative study by using LDI-MS, MALDI-MS, PESI-MS and ESI-MS.

PubMed

Petroselli, Gabriela; Mandal, Mridul Kanti; Chen, Lee Chuin; Ruiz, Gustavo T; Wolcan, Ezequiel; Hiraoka, Kenzo; Nonami, Hiroshi; Erra-Balsells, Rosa

2012-03-01

A group of rhenium (I) complexes including in their structure ligands such as CF(3)SO(3)-, CH(3)CO(2)-, CO, 2,2'-bipyridine, dipyridil[3,2-a:2'3'-c]phenazine, naphthalene-2-carboxylate, anthracene-9-carboxylate, pyrene-1-carboxylate and 1,10-phenanthroline have been studied for the first time by mass spectrometry. The probe electrospray ionization (PESI) is a technique based on electrospray ionization (ESI) that generates electrospray from the tip of a solid metal needle. In this work, mass spectra for organometallic complexes obtained by PESI were compared with those obtained by classical ESI and high flow rate electrospray ionization assisted by corona discharge (HF-ESI-CD), an ideal method to avoid decomposition of the complexes and to induce their oxidation to yield intact molecular cation radicals in gas state [M](+·) and to produce their reduction yielding the gas species [M](-·). It was found that both techniques showed in general the intact molecular ions of the organometallics studied and provided additional structure characteristic diagnostic fragments. As the rhenium complexes studied in the present work showed strong absorption in the UV-visible region, particularly at 355 nm, laser desorption ionization (LDI) mass spectrometry experiments could be conducted. Although intact molecular ions could be detected in a few cases, LDI mass spectra showed diagnostic fragments for characterization of the complexes structure. Furthermore, matrix-assisted laser desorption ionization (MALDI) mass spectra were obtained. Nor-harmane, a compound with basic character, was used as matrix, and the intact molecular ions were detected in two examples, in negative ion mode as the [M](-·) species. Results obtained with 2-[(2E)-3-(4-tert-buthylphenyl)-2-methylprop-2-enylidene] malononitrile (DCTB) as matrix are also described. LDI experiments provided more information about the rhenium complex structures than did the MALDI ones. Copyright © 2012 John Wiley & Sons, Ltd.

Smoke alarm and battery function 42 months after installation: a randomized trial.

PubMed

Peek-Asa, Corinne; Yang, Jingzhen; Hamann, Cara; Jones, Michael P; Young, Tracy; Zwerling, Craig

2010-10-01

This randomized trial presents findings from the longest follow-up study of smoke alarm and battery function to date. The purpose of this study is to examine differences in long-term function of smoke alarm and battery combinations. A total of 691 households in an ongoing cohort study were randomly allocated into smoke alarm groups of ionizing and photoelectric and battery groups of zinc and lithium. Smoke alarm function was measured in 633 (91.6%) households from January 2007 through February 2008, 42 months following original smoke alarm/battery installation. Data analyses were conducted in 2009. After 3.5 years, 81.9% of the 1898 smoke alarms were functional. Ionizing alarms with zinc batteries were the least likely to function (72.7%). In comparison, photoelectric alarms with lithium batteries were 2.9 times (95% CI=1.8, 4.5) more likely to function; ionizing alarms with lithium batteries were 2.0 times (95% CI=1.3, 3.1) more likely to function; and photoelectric alarms with zinc batteries were 1.7 times (95% CI=1.1, 2.5) more likely to function. Functionality was strongly tied to number of reports of nuisance alarms, which was higher for ionizing than photoelectric alarms. Photoelectric smoke alarms and lithium batteries are the most likely to function long after smoke alarm installation, and may be worthwhile investments despite their increased cost. Copyright © 2010 American Journal of Preventive Medicine. Published by Elsevier Inc. All rights reserved.

Synthesis of a Fucosylated Trisaccharide Via Transglycosylation by α-L-Fucosidase from Thermotoga maritima.

PubMed

Guzmán-Rodríguez, Francisco; Alatorre-Santamaría, Sergio; Gómez-Ruiz, Lorena; Rodríguez-Serrano, Gabriela; García-Garibay, Mariano; Cruz-Guerrero, Alma

2018-05-02

Fucosylated oligosaccharides, such as 2'-fucosyllactose in human milk, have important biological functions such as prebiotics and preventing infection. In this work, the effect of an acceptor substrate (lactose) and the donor substrate 4-nitrophenyl-α-L-fucopyranoside (pNP-Fuc) on the synthesis of a fucosylated trisaccharide was studied in a transglycosylation reaction using α-L-fucosidase from Thermotoga maritima. Conducting a matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF MS), it was demonstrated that synthesized oligosaccharide corresponded to a fucosylated trisaccharide, and high-performance liquid chromatography (HPLC) of the hydrolyzed compound confirmed it was fucosyllactose. As the concentration of the acceptor substrate increased, the concentration and synthesis rate of the fucosylated trisaccharide also increased, and the highest concentration obtained was 0.883 mM (25.2% yield) when using the higher initial lactose concentration (584 mM). Furthermore, the lower donor/acceptor ratio had the highest synthesis, so at the molar ratio of 0.001, a concentration of 0.286 mM was obtained (32.5% yield).

Simultaneous detection of low and high molecular weight carbonylated compounds derived from lipid peroxidation by electrospray ionization-tandem mass spectrometry.

PubMed

Milic, Ivana; Hoffmann, Ralf; Fedorova, Maria

2013-01-02

Reactive oxygen species (ROS) and other oxidative agents such as free radicals can oxidize polyunsaturated fatty acids (PUFA) as well as PUFA in lipids. The oxidation products can undergo consecutive reactions including oxidative cleavages to yield a chemically diverse group of products, such as lipid peroxidation products (LPP). Among them are aldehydes and ketones ("reactive carbonyls") that are strong electrophiles and thus can readily react with nucleophilic side chains of proteins, which can alter the protein structure, function, cellular distribution, and antigenicity. Here, we report a novel technique to specifically derivatize both low molecular and high molecular weight carbonylated LPP with 7-(diethylamino)coumarin-3-carbohydrazide (CHH) and analyze all compounds by electrospray ionization-mass spectrometry (ESI-MS) in positive ion mode. CHH-derivatized compounds were identified by specific neutral losses or fragment ions. The fragment ion spectra displayed additional signals that allowed unambiguous identification of the lipid, fatty acids, cleavage sites, and oxidative modifications. Oxidation of docosahexaenoic (DHA, 22:6), arachidonic (AA, 20:4), linoleic (LA, 18:2), and oleic acids (OA, 18:1) yielded 69 aliphatic carbonyls, whose structures were all deduced from the tandem mass spectra. When four phosphatidylcholine (PC) vesicles containing the aforementioned unsaturated fatty acids were oxidized, we were able to deduce the structures of 122 carbonylated compounds from the tandem mass spectra of a single shotgun analysis acquired within 15 min. The high sensitivity (LOD ∼ 1 nmol/L for 4-hydroxy-2-nonenal, HNE) and a linear range of more than 3 orders of magnitude (10 nmol/L to 10 μmol/L for HNE) will allow further studies on complex biological samples including plasma.

Electron-electron interaction in ion-atom collisions studied by projectile state-resolved Auger-electron spectroscopy

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

Dohyung Lee.

This dissertation addresses the problem of dynamic electron-electron interactions in fast ion-atom collisions using projectile Auger electron spectroscopy. The study was carried out by measuring high-resolution projectile KKL Auger electron spectra as a function of projectile energy for the various collision systems of 0.25-2 MeV/u O{sup q+} and F{sup q+} incident on H{sub 2} and He targets. The electrons were detected in the beam direction, where the kinematic broadening is minimized. A zero-degree tandem electron spectrometer system, was developed and showed the versatility of zero-degree measurements of collisionally-produced atomic states. The zero-degree binary encounter electrons (BEe), quasifree target electrons ionizedmore » by the projectiles in head-on collisions, were observed as a strong background in the KLL Auger electron spectrum. They were studied by treating the target ionization as 180{degree} Rutherford elastic scattering in the projectile frame, and resulted in a validity test of the impulse approximation (IA) and a way to determine the spectrometer efficiency. An anomalous q-dependence, in which the zero-degree BEe yields increase with decreasing projectile charge state (q), was observed. State-resolved KLL Auger cross sections were determined by using the BEe normalization and thus the cross section of the electron-electron interactions such as resonant transfer-excitation (RTE), electron-electron excitation (eeE), and electron-electron ionization (eeI) were determined. Projectile 2l capture with 1s {yields} 2p excitation by the captured target electron was observed as an RTE process with Li-like and He-like projectiles and the measured RTEA (RTE followed by Auger decay) cross sections showed good agreement with an RTE-IA treatment and RTE alignment theory.« less

Effect of neutrino rest mass on ionization equilibrium freeze-out

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

Grohs, Evan Bradley; Fuller, George M.; Kishimoto, Chad T.

2015-12-23

We show how small neutrino rest masses can increase the expansion rate near the photon decoupling epoch in the early Universe, causing an earlier, higher temperature freeze-out for ionization equilibrium compared to the massless neutrino case. This yields a larger free-electron fraction, thereby affecting the photon diffusion length differently than the sound horizon at photon decoupling. This neutrino-mass and recombination effect depends strongly on the neutrino rest masses. Ultimately, though below current sensitivity, this effect could be probed by next-generation cosmic microwave background experiments, giving another observational handle on neutrino rest mass.

Phase transition to an opaque plasma in a sonoluminescing bubble.

PubMed

Kappus, Brian; Khalid, Shahzad; Chakravarty, Avik; Putterman, Seth

2011-06-10

Time-resolved spectrum measurements of a sonoluminescing Xe bubble reveal a transition from transparency to an opaque Planck blackbody. As the temperature is <10 000  K and the density is below liquid density, the photon scattering length is 10 000 times too large to explain its opacity. We resolve this issue with a model that reduces the ionization potential. According to this model, sonoluminescence originates in a new phase of matter with high ionization. Analysis of line emission from Xe* also yields evidence of phase segregation for this first-order transition inside a bubble.

Inclusion of Theta(12) dependence in the Coulomb-dipole theory of the ionization threshold

NASA Technical Reports Server (NTRS)

Srivastava, M. K.; Temkin, A.

1991-01-01

The Coulomb-dipole (CD) theory of the electron-atom impact-ionization threshold law is extended to include the full electronic repulsion. It is found that the threshold law is altered to a form in contrast to the previous angular-independent model. A second energy regime, is also identified wherein the 'threshold' law reverts to its angle-independent form. In the final part of the paper the dipole parameter is estimated to be about 28. This yields numerical estimates of E(a) = about 0.0003 and E(b) = about 0.25 eV.

Threshold law for positron-atom impact ionisation

NASA Technical Reports Server (NTRS)

Temkin, A.

1982-01-01

The threshold law for ionisation of atoms by positron impact is adduced in analogy with our approach to the electron-atom ionization. It is concluded the Coulomb-dipole region of the potential gives the essential part of the interaction in both cases and leads to the same kind of result: a modulated linear law. An additional process which enters positron ionization is positronium formation in the continuum, but that will not dominate the threshold yield. The result is in sharp contrast to the positron threshold law as recently derived by Klar on the basis of a Wannier-type analysis.

Problems in mechanistic theoretical models for cell transformation by ionizing radiation

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

Chatterjee, A.; Holley, W.R.

1991-10-01

A mechanistic model based on yields of double strand breaks has been developed to determine the dose response curves for cell transformation frequencies. At its present stage the model is applicable to immortal cell lines and to various qualities (X-rays, Neon and Iron) of ionizing radiation. Presently, we have considered four types of processes which can lead to activation phenomena: (1) point mutation events on a regulatory segment of selected oncogenes, (2) inactivation of suppressor genes, through point mutation, (3) deletion of a suppressor gene by a single track, and (4) deletion of a suppressor gene by two tracks.

Formic acid-based direct, on-plate testing of yeast and Corynebacterium species by Bruker Biotyper matrix-assisted laser desorption ionization-time of flight mass spectrometry.

PubMed

Theel, Elitza S; Schmitt, Bryan H; Hall, Leslie; Cunningham, Scott A; Walchak, Robert C; Patel, Robin; Wengenack, Nancy L

2012-09-01

An on-plate testing method using formic acid was evaluated on the Bruker Biotyper matrix-assisted laser desorption ionization-time of flight (MALDI-TOF) mass spectrometry system using 90 yeast and 78 Corynebacterium species isolates, and 95.6 and 81.1% of yeast and 96.1 and 92.3% of Corynebacterium isolates were correctly identified to the genus and species levels, respectively. The on-plate method using formic acid yielded identification percentages similar to those for the conventional but more laborious tube-based extraction.

Critical parameters, thermodynamic functions, and shock Hugoniot of aluminum fluid at high energy density

NASA Astrophysics Data System (ADS)

Zaghloul, Mofreh R.

2018-03-01

We present estimates of the critical properties, thermodynamic functions, and principal shock Hugoniot of hot dense aluminum fluid as predicted from a chemical model for the equation-of-state of hot dense, partially ionized and partially degenerate plasma. The essential features of strongly coupled plasma of metal vapors, such as multiple ionization, Coulomb interactions among charged particles, partial degeneracy, and intensive short range hard core repulsion are taken into consideration. Internal partition functions of neutral, excited, and multiply ionized species are carefully evaluated in a statistical-mechanically consistent way. Results predicted from the present model are presented, analyzed and compared with available experimental measurements and other theoretical predictions in the literature.

The Origins of Scintillator Non-Proportionality

NASA Astrophysics Data System (ADS)

Moses, W. W.; Bizarri, G. A.; Williams, R. T.; Payne, S. A.; Vasil'ev, A. N.; Singh, J.; Li, Q.; Grim, J. Q.; Choong, W.-S.

2012-10-01

Recent years have seen significant advances in both theoretically understanding and mathematically modeling the underlying causes of scintillator non-proportionality. The core cause is that the interaction of radiation with matter invariably leads to a non-uniform ionization density in the scintillator, coupled with the fact that the light yield depends on the ionization density. The mechanisms that lead to the luminescence dependence on ionization density are incompletely understood, but several important features have been identified, notably Auger-like processes (where two carriers of excitation interact with each other, causing one to de-excite non-radiatively), the inability of excitation carriers to recombine (caused either by trapping or physical separation), and the carrier mobility. This paper reviews the present understanding of the fundamental origins of scintillator non-proportionality, specifically the various theories that have been used to explain non-proportionality.

Randomized controlled trial of ionization and photoelectric smoke alarm functionality.

PubMed

Mueller, B A; Sidman, E A; Alter, H; Perkins, R; Grossman, D C

2008-04-01

To compare functionality, reasons for non-function, and nuisance alarm levels of two common types of smoke alarms after installation in low- to mid-level income households in King County, Washington. Randomized controlled trial of 761 households. An ionization or photoelectric smoke alarm was installed between June 1, 2000 and July 31, 2002. Main outcome measures were: percentage of study alarms that were working, observed reasons for non-functional status, and self-reported frequency of nuisance alarms at 9 and 15 months of follow-up. At 9 months after installation, 20% of ionization, vs 5% of photoelectric alarms were non-functional, a difference that persisted at 15 months, with the most common reasons for both types being a disconnected or absent battery. The risk ratio for ionization, relative to photoelectric alarms, being non-functional or removed was 2.7 (95% CI 1.8 to 4.1) at 15 months of follow-up. These findings were not altered by educational level, or the presence of smokers, children <5 years, or adults > or =65 years. Burn prevention efforts are geared towards increasing smoke alarm ownership and improving maintenance of functional status. Results suggest that the selective use of photoelectric alarms by fire injury prevention programs or consumers may provide longer-term protection in similar populations. Designing smoke alarms that minimize nuisance alarming may also result in longer term functionality.

Equation of state and shock compression of warm dense sodium—A first-principles study

DOE PAGES

Zhang, Shuai; Driver, Kevin P.; Soubiran, Francois; ...

2017-02-21

As one of the simple alkali metals, sodium has been of fundamental interest for shock physics experiments, but knowledge of its equation of state (EOS) in hot, dense regimes is not well known. By combining path integral Monte Carlo (PIMC) results for partially ionized states at high temperatures and density functional theory molecular dynamics (DFT-MD) results at lower temperatures, we have constructed a coherent equation of state for sodium over a wide density-temperature range of 1.93-11.60 g/cm 3 and 10 3–1.29×10 8 K. We find that a localized, Hartree-Fock nodal structure in PIMC yields pressures and internal energies that aremore » consistent with DFT-MD at intermediate temperatures of 2×10 6 K. Since PIMC and DFT-MD provide a first-principles treatment of electron shell and excitation effects, we are able to identify two compression maxima in the shock Hugoniot curve corresponding to K-shell and L-shell ionization. Our Hugoniot curves provide a benchmark for widely used EOS models: SESAME, LEOS, and Purgatorio. Due to the low ambient density, sodium has an unusually high first compression maximum along the shock Hugoniot curve. At beyond 10 7 K, we show that the radiation effect leads to very high compression along the Hugoniot curve, surpassing relativistic corrections, and observe an increasing deviation of the shock and particle velocities from a linear relation. Here, we also compute the temperature-density dependence of thermal and pressure ionization processes.« less

The effect of temperature on the stability of compounds used as UV-MALDI-MS matrix: 2,5-dihydroxybenzoic acid, 2,4,6-trihydroxyacetophenone, alpha-cyano-4-hydroxycinnamic acid, 3,5-dimethoxy-4-hydroxycinnamic acid, nor-harmane and harmane.

PubMed

Tarzi, Olga I; Nonami, Hiroshi; Erra-Balsells, Rosa

2009-02-01

The thermal stability of several commonly used crystalline matrix-assisted ultraviolet laser desorption/ionization mass spectrometry (UV-MALDI-MS) matrices, 2,5-dihydroxybenzoic acid (gentisic acid; GA), 2,4,6-trihydroxyacetophenone (THA), alpha-cyano-4-hydroxycinnamic acid (CHC), 3,5-dimethoxy-4-hydroxycinnamic acid (sinapinic acid; SA), 9H-pirido[3,4-b]indole (nor-harmane; nor-Ho), 1-methyl-9H-pirido[3,4-b]indole (harmane; Ho), perchlorate of nor-harmanonium ([nor-Ho+H]+) and perchlorate of harmanonium ([Ho+H]+) was studied by heating them at their melting point and characterizing the remaining material by using different MS techniques [electron ionization mass spectrometry (EI-MS), ultraviolet laserdesorption/ionization-time-of-flight-mass spectrometry (UV-LDI-TOF-MS) and electrospray ionization-time-of-flight-mass spectrometry (ESI-TOF-MS)] as well as by thin layer chromatography analysis (TLC), electronic spectroscopy (UV-absorption, fluorescence emission and excitation spectroscopy) and 1H nuclear magnetic resonance spectroscopy (1H-NMR). In general, all compounds, except for CHC and SA, remained unchanged after fusion. CHC showed loss of CO2, yielding the trans-/cis-4-hydroxyphenylacrilonitrile mixture. This mixture was unambiguously characterized by MS and 1H-NMR spectroscopy, and its sublimation capability was demonstrated. These results explain the well-known cluster formation, fading (vanishing) and further recovering of CHC when used as a matrix in UV-MALDI-MS. Commercial SA (SA 98%; trans-SA/cis-SA 5:1) showed mainly cis- to-trans thermal isomerization and, with very poor yield, loss of CO2, yielding (3',5'-dimethoxy-4'-hydroxyphenyl)-1-ethene as the decarboxilated product. These thermal conversions would not drastically affect its behavior as a UV-MALDI matrix as happens in the case of CHC. Complementary studies of the photochemical stability of these matrices in solid state were also conducted. Copyright (c) 2008 John Wiley & Sons, Ltd.

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

Gao, Fei; Kerisit, Sebastien N.; Xie, YuLong

This annual report presents work carried out during Fiscal Year (FY) 2013 at Pacific Northwest National Laboratory (PNNL) under the project entitled “Science-Driven Candidate Search for New Scintillator Materials” (Project number: PL13-SciDriScintMat-PD05) and led by Dr. Fei Gao. This project is divided into three tasks, namely (1) Ab initio calculations of electronic properties, electronic response functions and secondary particle spectra; (2) Intrinsic response properties, theoretical light yield, and microscopic description of ionization tracks; and (3) Kinetics and efficiency of scintillation: nonlinearity, intrinsic energy resolution, and pulse shape discrimination. Detailed information on the findings and insights obtained in each of thesemore » three tasks are provided in this report. Additionally, papers published this fiscal year or currently in review are included in Appendix together with presentations given this fiscal year.« less

Thermodynamics and Charging of Interstellar Iron Nanoparticles

NASA Astrophysics Data System (ADS)

Hensley, Brandon S.; Draine, B. T.

2017-01-01

Interstellar iron in the form of metallic iron nanoparticles may constitute a component of the interstellar dust. We compute the stability of iron nanoparticles to sublimation in the interstellar radiation field, finding that iron clusters can persist down to a radius of ≃4.5 Å, and perhaps smaller. We employ laboratory data on small iron clusters to compute the photoelectric yields as a function of grain size and the resulting grain charge distribution in various interstellar environments, finding that iron nanoparticles can acquire negative charges, particularly in regions with high gas temperatures and ionization fractions. If ≳10% of the interstellar iron is in the form of ultrasmall iron clusters, the photoelectric heating rate from dust may be increased by up to tens of percent relative to dust models with only carbonaceous and silicate grains.

Investigation of Ozone Yield of Air Fed Ozonizer by High Pressure Homogeneous Dielectric Barrier Discharge

DTIC Science & Technology

2013-07-01

31st ICPIG, July 14-19, 2013, Granada , Spain Investigation of ozone yield of air fed ozonizer by high pressure homogeneous dielectric barrier...Phenomena in Ionized Gases (31st) (ICPIG) Held in Granada , Spain on 14-19 July 2013 14. ABSTRACT We succeed in generating an atmospheric and high...8-98) Prescribed by ANSI Std Z39-18 31st ICPIG, July 14-19, 2013, Granada , Spain size and thickness are 100 cm2 and 2 mm respectively. The

Poem: A Fast Monte Carlo Code for the Calculation of X-Ray Transition Zone Dose and Current

DTIC Science & Technology

1975-01-15

stored on the photon interaction data tape. Following the photoelectric ionization the atom will relax emitting either a fluorescent photon or an Auger 50...shell fluorescence yield CL have been obtained from the Storm and Israel1 9 and 25 Bambynek, et al. compilations, with preference given to the...Bambynek compilation, and stored on the photon inter- action data tape. The mean M fluorescence yield wM is approximated by zero. The total electron source

Space experiments with particle accelerators

NASA Technical Reports Server (NTRS)

Obayashi, T.; Kawashima, N.; Kuriki, K.; Nagatomo, M.; Ninomiya, K.; Sasaki, S.; Roberts, W. T.; Chappell, C. R.; Reasoner, D. L.; Garriott, O. K.;

Fast Atom Bombardment Mass Spectrometry.

ERIC Educational Resources Information Center

Rinehart, Kenneth L., Jr.

1982-01-01

Discusses reactions and characteristics of fast atom bombardment (FAB) mass spectroscopy in which samples are ionized in a condensed state by bombardment with xenon or argon atoms, yielding positive/negative secondary ions. Includes applications of FAB to structural problems and considers future developments using the technique. (Author/JN)

Analysis of trace fibers by IR-MALDESI imaging coupled with high resolving power MS

PubMed Central

Cochran, Kristin H.; Barry, Jeremy A.; Robichaud, Guillaume

2016-01-01

Trace evidence is a significant portion of forensic cases. Textile fibers are a common form of trace evidence that are gaining importance in criminal cases. Currently, qualitative techniques that do not yield structural information are primarily used for fiber analysis, but mass spectrometry is gaining an increasing role in this field. Mass spectrometry yields more quantitative structural information about the dye and polymer that can be used for more conclusive comparisons. Matrix-assisted laser desorption electrospray ionization (MALDESI) is a hybrid ambient ionization source being investigated for use in mass spectrometric fiber analysis. In this manuscript, IR-MALDESI was used as a source for mass spectrometry imaging (MSI) of a dyed nylon fiber cluster and single fiber. Information about the fiber polymer as well as the dye were obtained from a single fiber which was on the order of 10 μm in diameter. These experiments were performed directly from the surface of a tape lift of the fiber with a background of extraneous fibers. PMID:25081013

Analysis of trace fibers by IR-MALDESI imaging coupled with high resolving power MS.

PubMed

Cochran, Kristin H; Barry, Jeremy A; Robichaud, Guillaume; Muddiman, David C

2015-01-01

Trace evidence is a significant portion of forensic cases. Textile fibers are a common form of trace evidence that are gaining importance in criminal cases. Currently, qualitative techniques that do not yield structural information are primarily used for fiber analysis, but mass spectrometry is gaining an increasing role in this field. Mass spectrometry yields more quantitative structural information about the dye and polymer that can be used for more conclusive comparisons. Matrix-assisted laser desorption electrospray ionization (MALDESI) is a hybrid ambient ionization source being investigated for use in mass spectrometric fiber analysis. In this manuscript, IR-MALDESI was used as a source for mass spectrometry imaging (MSI) of a dyed nylon fiber cluster and single fiber. Information about the fiber polymer as well as the dye were obtained from a single fiber which was on the order of 10 μm in diameter. These experiments were performed directly from the surface of a tape lift of the fiber with a background of extraneous fibers.

Radiation induced degradation of xanthan gum in aqueous solution

NASA Astrophysics Data System (ADS)

Hayrabolulu, Hande; Demeter, Maria; Cutrubinis, Mihalis; Güven, Olgun; Şen, Murat

2018-03-01

In our previous study, we have investigated the effect of gamma rays on xanthan gum in the solid state and it was determined that dose rate was an important factor effecting the radiation degradation of xanthan gum. In the present study, in order to provide a better understanding of how ionizing radiation effect xanthan gum, we have investigated the effects of ionizing radiation on aqueous solutions of xanthan at various concentrations (0.5-4%). Xanthan solutions were irradiated with gamma rays in air, at ambient temperature, at different dose rates (0.1-3.3-7.0 kGy/h) and doses (2.5-50 kGy). Change in their molecular weights was followed by size exclusion chromatography (SEC). Chain scission yield (G(S)), and degradation rate constants (k) were calculated. It was determined that, solution concentration was a factor effecting the degradation chemical yield and degradation rate of xanthan gum. Chain scission reactions were more effective for lower solution concentrations.

Quasar outflows and AGN feedback in the extreme UV: HST/COS observations of HE 0238-1904

NASA Astrophysics Data System (ADS)

Arav, Nahum; Borguet, Benoit; Chamberlain, Carter; Edmonds, Doug; Danforth, Charles

2013-12-01

Spectroscopic observations of quasar outflows at rest-frame 500-1000 Å have immense diagnostic power. We present analyses of such data, where absorption troughs from O IV and O IV* allow us to obtain the distance of the outflows from the AGN and troughs from Ne VIII and Mg X reveal the warm absorber phase of the outflow. Their inferred column densities, combined with those of O VI, N IV and H I, yield two important results. (1) The outflow shows two ionization phases, where the high-ionization phase carries the bulk of the material. This is similar to the situation seen in X-ray warm absorber studies. Furthermore, the low-ionization phase is inferred to have a volume filling factor of 10-5-10-6. (2) We determine a distance of 3000 pc from the outflow to the central source using the O IV*/O IV column density ratio and the knowledge of the ionization parameter. Since this is a typical high-ionization outflow, we can determine robust values for the outflow's mass flux and kinetic luminosity of 40 M⊙ yr-1 and 1045 erg s-1, respectively, where the latter is roughly equal to 1 per cent of the bolometric luminosity. Such a large kinetic luminosity and mass flow rate measured in a typical high-ionization wind suggest that quasar outflows are a major contributor to AGN feedback mechanisms.

Multielectron effects in the photoelectron momentum distribution of noble-gas atoms driven by visible-to-infrared-frequency laser pulses: A time-dependent density-functional-theory approach

NASA Astrophysics Data System (ADS)

Murakami, Mitsuko; Zhang, G. P.; Chu, Shih-I.

2017-05-01

We present the photoelectron momentum distributions (PMDs) of helium, neon, and argon atoms driven by a linearly polarized, visible (527-nm) or near-infrared (800-nm) laser pulse (20 optical cycles in duration) based on the time-dependent density-functional theory (TDDFT) under the local-density approximation with a self-interaction correction. A set of time-dependent Kohn-Sham equations for all electrons in an atom is numerically solved using the generalized pseudospectral method. An effect of the electron-electron interaction driven by a visible laser field is not recognizable in the helium and neon PMDs except for a reduction of the overall photoelectron yield, but there is a clear difference between the PMDs of an argon atom calculated with the frozen-core approximation and TDDFT, indicating an interference of its M -shell wave functions during the ionization. Furthermore, we find that the PMDs of degenerate p states are well separated in intensity when driven by a near-infrared laser field, so that the single-active-electron approximation can be adopted safely.

Microplume model of spatial-yield spectra. [applying to electron gas degradation in molecular nitrogen gas

NASA Technical Reports Server (NTRS)

Green, A. E. S.; Singhal, R. P.

1979-01-01

An analytic representation for the spatial (radial and longitudinal) yield spectra is developed in terms of a model containing three simple 'microplumes'. The model is applied to electron energy degradation in molecular nitrogen gas for 0.1 to 5 keV incident electrons. From the nature of the cross section input to this model it is expected that the scaled spatial yield spectra for other gases will be quite similar. The model indicates that each excitation, ionization, etc. plume should have its individual spatial and energy dependence. Extensions and aeronomical and radiological applications of the model are discussed.

Effects of molecular weight and cationization agent on the sensitivity of Bi cluster secondary ion mass spectrometry.

PubMed

Fujii, Makiko; Shishido, Rie; Satoh, Takaya; Suzuki, Shigeru; Matsuo, Jiro

2016-07-30

Bi cluster secondary ion mass spectrometry (SIMS) is one of the most promising tools for precise analysis of synthetic polymers. However, the sensitivity in the high-mass region is still insufficient compared with matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOFMS). Accordingly, the effects of metal assistance (cationization agents) were investigated in this study. To investigate the effects caused by varying the ionization agent, three different polyethylene glycol (PEG) samples were prepared, one with an Ag-deposited film, and two others mixed with Ag and Na, respectively. The measurements were performed by using a commercial Bi cluster SIMS and MALDI-TOFMS systems. The mass spectrum obtained with MALDI-TOFMS was used as a reference molecular weight distribution to evaluate the effects of molecular weight and primary ion species (Bi + , Bi 3 + , Bi 3 2 + ) on the sensitivity of Bi cluster SIMS. The intensity of each secondary ion was the highest in Bi 3 2 + irradiation, and the lowest in Bi + irradiation. Regarding the cationization agents, the secondary ion yield was the highest for the sample mixed with Ag, while the degree of decay of sensitivity along with the increase in molecular weight was the smallest for the sample mixed with Na. It was suggested that the cationization mechanism consists of pre-formed ionization and gas-phase ionization processes. The sensitivity of Bi cluster SIMS decreases to approximately one-fiftieth in every 1000 u. These results might help in understanding the mechanism of cationization and further enhancement of secondary ion yields of polymers. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

Study of dust particle charging in weakly ionized inert gases taking into account the nonlocality of the electron energy distribution function

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

Filippov, A. V., E-mail: fav@triniti.ru; Dyatko, N. A.; Kostenko, A. S.

2014-11-15

The charging of dust particles in weakly ionized inert gases at atmospheric pressure has been investigated. The conditions under which the gas is ionized by an external source, a beam of fast electrons, are considered. The electron energy distribution function in argon, krypton, and xenon has been calculated for three rates of gas ionization by fast electrons: 10{sup 13}, 10{sup 14}, and 10{sup 15} cm{sup −1}. A model of dust particle charging with allowance for the nonlocal formation of the electron energy distribution function in the region of strong plasma quasi-neutrality violation around the dust particle is described. The nonlocalitymore » is taken into account in an approximation where the distribution function is a function of only the total electron energy. Comparative calculations of the dust particle charge with and without allowance for the nonlocality of the electron energy distribution function have been performed. Allowance for the nonlocality is shown to lead to a noticeable increase in the dust particle charge due to the influence of the group of hot electrons from the tail of the distribution function. It has been established that the screening constant virtually coincides with the smallest screening constant determined according to the asymptotic theory of screening with the electron transport and recombination coefficients in an unperturbed plasma.« less

Theory of dissociative tunneling ionization

NASA Astrophysics Data System (ADS)

Svensmark, Jens; Tolstikhin, Oleg I.; Madsen, Lars Bojer

2016-05-01

We present a theoretical study of the dissociative tunneling ionization process. Analytic expressions for the nuclear kinetic energy distribution of the ionization rates are derived. A particularly simple expression for the spectrum is found by using the Born-Oppenheimer (BO) approximation in conjunction with the reflection principle. These spectra are compared to exact non-BO ab initio spectra obtained through model calculations with a quantum mechanical treatment of both the electronic and nuclear degrees of freedom. In the regime where the BO approximation is applicable, imaging of the BO nuclear wave function is demonstrated to be possible through reverse use of the reflection principle, when accounting appropriately for the electronic ionization rate. A qualitative difference between the exact and BO wave functions in the asymptotic region of large electronic distances is shown. Additionally, the behavior of the wave function across the turning line is seen to be reminiscent of light refraction. For weak fields, where the BO approximation does not apply, the weak-field asymptotic theory describes the spectrum accurately.

An X-Ray Analysis Database of Photoionization Cross Sections Including Variable Ionization

NASA Technical Reports Server (NTRS)

Wang, Ping; Cohen, David H.; MacFarlane, Joseph J.; Cassinelli, Joseph P.

1997-01-01

Results of research efforts in the following areas are discussed: review of the major theoretical and experimental data of subshell photoionization cross sections and ionization edges of atomic ions to assess the accuracy of the data, and to compile the most reliable of these data in our own database; detailed atomic physics calculations to complement the database for all ions of 17 cosmically abundant elements; reconciling the data from various sources and our own calculations; and fitting cross sections with functional approximations and incorporating these functions into a compact computer code.Also, efforts included adapting an ionization equilibrium code, tabulating results, and incorporating them into the overall program and testing the code (both ionization equilibrium and opacity codes) with existing observational data. The background and scientific applications of this work are discussed. Atomic physics cross section models and calculations are described. Calculation results are compared with available experimental data and other theoretical data. The functional approximations used for fitting cross sections are outlined and applications of the database are discussed.

Electron impact ionization in the vicinity of comets

NASA Astrophysics Data System (ADS)

Cravens, T. E.; Kozyra, J. U.; Nagy, A. F.; Gombosi, T. I.; Kurtz, M.

1987-07-01

The solar wind interacts very strongly with the extensive cometary coma, and the various interaction processes are initiated by the ionization of cometary neutrals. The main ionization mechanism far outside the cometary bow shock is photoionization by solar extreme ultraviolet radiation.Electron distributions measured in the vicinity of comets Halley and Giacobini-Zinner by instruments on the VEGA and ICE spacecraft, respectively, are used to calculate electron impact ionization frequencies. Ionization by electrons is of comparable importance to photoionization in the magnetosheaths of Comets Halley and Giacobini-Zinner. The ionization frequency in the inner part of the cometary plasma region of comet Halley is several times greater than the photoionization value. Tables of ionization frequencies as functions of electron temperature are presented for H2O, CO2, CO, O, N2, and H.

Progress in Studying Scintillator Proportionality: Phenomenological Model

NASA Astrophysics Data System (ADS)

Bizarri, G.; Cherepy, N. J.; Choong, W. S.; Hull, G.; Moses, W. W.; Payne, S. A.; Singh, J.; Valentine, J. D.; Vasilev, A. N.; Williams, R. T.

2009-08-01

We present a model to describe the origin of non-proportional dependence of scintillator light yield on the energy of an ionizing particle. The non-proportionality is discussed in terms of energy relaxation channels and their linear and non-linear dependences on the deposited energy. In this approach, the scintillation response is described as a function of the deposited energy deposition and the kinetic rates of each relaxation channel. This mathematical framework allows both a qualitative interpretation and a quantitative fitting representation of scintillation non-proportionality response as function of kinetic rates. This method was successfully applied to thallium doped sodium iodide measured with SLYNCI, a new facility using the Compton coincidence technique. Finally, attention is given to the physical meaning of the dominant relaxation channels, and to the potential causes responsible for the scintillation non-proportionality. We find that thallium doped sodium iodide behaves as if non-proportionality is due to competition between radiative recombinations and non-radiative Auger processes.

Single impacts of keV fullerene ions on free standing graphene: Emission of ions and electrons from confined volume

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

Verkhoturov, Stanislav V.; Geng, Sheng; Schweikert, Emile A., E-mail: schweikert@chem.tamu.edu

We present the first data from individual C{sub 60} impacting one to four layer graphene at 25 and 50 keV. Negative secondary ions and electrons emitted in transmission were recorded separately from each impact. The yields for C{sub n}{sup −} clusters are above 10% for n ≤ 4, they oscillate with electron affinities and decrease exponentially with n. The result can be explained with the aid of MD simulation as a post-collision process where sufficient vibrational energy is accumulated around the rim of the impact hole for sputtering of carbon clusters. The ionization probability can be estimated by comparing experimentalmore » yields of C{sub n}{sup −} with those of C{sub n}{sup 0} from MD simulation, where it increases exponentially with n. The ionization probability can be approximated with ejecta from a thermally excited (3700 K) rim damped by cluster fragmentation and electron detachment. The experimental electron probability distributions are Poisson-like. On average, three electrons of thermal energies are emitted per impact. The thermal excitation model invoked for C{sub n}{sup −} emission can also explain the emission of electrons. The interaction of C{sub 60} with graphene is fundamentally different from impacts on 3D targets. A key characteristic is the high degree of ionization of the ejecta.« less

Tracking dissociation dynamics of strong-field ionized 1,2-dibromoethane with femtosecond XUV transient absorption spectroscopy.

PubMed

Chatterley, Adam S; Lackner, Florian; Neumark, Daniel M; Leone, Stephen R; Gessner, Oliver

2016-06-07

Using femtosecond time-resolved extreme ultraviolet absorption spectroscopy, the dissociation dynamics of the haloalkane 1,2-dibromoethane (DBE) have been explored following strong field ionization by femtosecond near infrared pulses at intensities between 7.5 × 10(13) and 2.2 × 10(14) W cm(-2). The major elimination products are bromine atoms in charge states of 0, +1, and +2. The charge state distribution is strongly dependent on the incident NIR intensity. While the yield of neutral fragments is essentially constant for all measurements, charged fragment yields grow rapidly with increasing NIR intensities with the most pronounced effect observed for Br(++). However, the appearance times of all bromine fragments are independent of the incident field strength; these are found to be 320 fs, 70 fs, and 30 fs for Br˙, Br(+), and Br(++), respectively. Transient molecular ion features assigned to DBE(+) and DBE(++) are observed, with dynamics linked to the production of Br(+) products. Neutral Br˙ atoms are produced on a timescale consistent with dissociation of DBE(+) ions on a shallow potential energy surface. The appearance of Br(+) ions by dissociative ionization is also seen, as evidenced by the simultaneous decay of a DBE(+) ionic species. Dicationic Br(++) products emerge within the instrument response time, presumably from Coulomb explosion of triply charged DBE.

Tracking dissociation dynamics of strong-field ionized 1,2-dibromoethane with femtosecond XUV transient absorption spectroscopy

DOE PAGES

Chatterley, Adam S.; Lackner, Florian; Neumark, Daniel M.; ...

2016-05-11

Using femtosecond time-resolved extreme ultraviolet absorption spectroscopy, the dissociation dynamics of the haloalkane 1,2-dibromoethane (DBE) have been explored following strong field ionization by femtosecond near infrared pulses at intensities between 7.5 × 10 13 and 2.2 × 10 14 W cm -2. The major elimination products are bromine atoms in charge states of 0, +1, and +2. The charge state distribution is strongly dependent on the incident NIR intensity. While the yield of neutral fragments is essentially constant for all measurements, charged fragment yields grow rapidly with increasing NIR intensities with the most pronounced effect observed for Br ++. However,more » the appearance times of all bromine fragments are independent of the incident field strength; these are found to be 320 fs, 70 fs, and 30 fs for Br˙, Br +, and Br ++, respectively. Transient molecular ion features assigned to DBE + and DBE ++ are observed, with dynamics linked to the production of Br + products. Neutral Br˙ atoms are produced on a timescale consistent with dissociation of DBE + ions on a shallow potential energy surface. The appearance of Br + ions by dissociative ionization is also seen, as evidenced by the simultaneous decay of a DBE + ionic species. Dicationic Br ++ products emerge within the instrument response time, presumably from Coulomb explosion of triply charged DBE.« less

Transverse Space-Charge Field-Induced Plasma Dynamics for Ultraintense Electron-Beam Characterization

NASA Astrophysics Data System (ADS)

Tarkeshian, R.; Vay, J. L.; Lehe, R.; Schroeder, C. B.; Esarey, E. H.; Feurer, T.; Leemans, W. P.

2018-04-01

Similarly to laser or x-ray beams, the interaction of sufficiently intense particle beams with neutral gases will result in the creation of plasma. In contrast to photon-based ionization, the strong unipolar field of a particle beam can generate a plasma where the electron population receives a large initial momentum kick and escapes, leaving behind unshielded ions. Measuring the properties of the ensuing Coulomb exploding ions—such as their kinetic energy distribution, yield, and spatial distribution—can provide information about the peak electric fields that are achieved in the electron beams. Particle-in-cell simulations and analytical models are presented for high-brightness electron beams of a few femtoseconds or even hundreds of attoseconds, and transverse beam sizes on the micron scale, as generated by today's free electron lasers. Different density regimes for the utilization as a potential diagnostics are explored, and the fundamental differences in plasma dynamical behavior for e-beam or photon-based ionization are highlighted. By measuring the dynamics of field-induced ions for different gas and beam densities, a lower bound on the beam charge density can be obtained in a single shot and in a noninvasive way. The exponential dependency of the ionization yield on the beam properties can provide unprecedented spatial and temporal resolution, at the submicrometer and subfemtosecond scales, respectively, offering a practical and powerful approach to characterizing beams from accelerators at the frontiers of performance.

Useful ion yields for Cameca IMS 3f and 6f SIMS: Limits on quantitative analysis

USGS Publications Warehouse

Hervig, R.L.; Mazdab, F.K.; Williams, Pat; Guan, Y.; Huss, G.R.; Leshin, L.A.

2006-01-01

The useful yields (ions detected/atom sputtered) of major and trace elements in NIST 610 glass were measured by secondary ion mass spectrometry (SIMS) using Cameca IMS 3f and 6f instruments. Useful yields of positive ions at maximum transmission range from 10-4 to 0.2 and are negatively correlated with ionization potential. We quantified the decrease in useful yields when applying energy filtering or high mass resolution techniques to remove molecular interferences. The useful yields of selected negative ions (O, S, Au) in magnetite and pyrite were also determined. These data allow the analyst to determine if a particular analysis (trace element contents or isotopic ratio) can be achieved, given the amount of sample available and the conditions of the analysis. ?? 2005 Elsevier B.V. All rights reserved.

In-gas-cell laser ionization studies of plutonium isotopes at IGISOL

NASA Astrophysics Data System (ADS)

Pohjalainen, I.; Moore, I. D.; Kron, T.; Raeder, S.; Sonnenschein, V.; Tomita, H.; Trautmann, N.; Voss, A.; Wendt, K.

2016-06-01

In-gas-cell resonance laser ionization has been performed on long-lived isotopes of Pu at the IGISOL facility, Jyväskylä. This initiates a new programme of research towards high-resolution optical spectroscopy of heavy actinide elements which can be produced in sufficient quantities at research reactors and transported to facilities elsewhere. In this work a new gas cell has been constructed for fast extraction of laser-ionized elements. Samples of 238-240,242Pu and 244Pu have been evaporated from Ta filaments, laser ionized, mass separated and delivered to the collinear laser spectroscopy station. Here we report on the performance of the gas cell through studies of the mass spectra obtained in helium and argon, before and after the radiofrequency quadrupole cooler-buncher. This provides valuable insight into the gas phase chemistry exhibited by Pu, which has been additionally supported by measurements of ion time profiles. The resulting monoatomic yields are sufficient for collinear laser spectroscopy. A gamma-ray spectroscopic analysis of the Pu samples shows a good agreement with the assay provided by the Mainz Nuclear Chemistry department.

Modification of the quantum mechanical flux formula for electron-hydrogen ionization through Bohm's velocity field

NASA Astrophysics Data System (ADS)

Randazzo, J. M.; Ancarani, L. U.

2015-12-01

For the single differential cross section (SDCS) for hydrogen ionization by electron impact (e -H problem), we propose a correction to the flux formula given by R. Peterkop [Theory of Ionization of Atoms by Electron Impact (Colorado Associated University Press, Boulder, 1977)]. The modification is based on an alternative way of defining the kinetic energy fraction, using Bohm's definition of velocities instead of the usual asymptotic kinematical, or geometrical, approximation. It turns out that the solution-dependent, modified energy fraction is equally related to the components of the probability flux. Compared to what is usually observed, the correction yields a finite and well-behaved SDCS value in the asymmetrical situation where one of the continuum electrons carries all the energy while the other has zero energy. We also discuss, within the S -wave model of the e -H ionization process, the continuity of the SDCS derivative at the equal energy sharing point, a property not so clearly observed in published benchmark results obtained with integral and S -matrix formulas with unequal final states.

Quasistatic limit of the strong-field approximation describing atoms in intense laser fields: Circular polarization

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

Bauer, Jaroslaw H.

2011-03-15

In the recent work of Vanne and Saenz [Phys. Rev. A 75, 063403 (2007)] the quasistatic limit of the velocity gauge strong-field approximation describing the ionization rate of atomic or molecular systems exposed to linearly polarized laser fields was derived. It was shown that in the low-frequency limit the ionization rate is proportional to the laser frequency {omega} (for a constant intensity of the laser field). In the present work I show that for circularly polarized laser fields the ionization rate is proportional to {omega}{sup 4} for H(1s) and H(2s) atoms, to {omega}{sup 6} for H(2p{sub x}) and H(2p{sub y})more » atoms, and to {omega}{sup 8} for H(2p{sub z}) atoms. The analytical expressions for asymptotic ionization rates (which become nearly accurate in the limit {omega}{yields}0) contain no summations over multiphoton contributions. For very low laser frequencies (optical or infrared) these expressions usually remain with an order-of-magnitude agreement with the velocity gauge strong-field approximation.« less

Atmospheric helium and geomagnetic field reversals.

NASA Technical Reports Server (NTRS)

Sheldon, W. R.; Kern, J. W.

1972-01-01

The problem of the earth's helium budget is examined in the light of recent work on the interaction of the solar wind with nonmagnetic planets. It is proposed that the dominant mode of helium (He4) loss is ion pumping by the solar wind during geomagnetic field reversals, when the earth's magnetic field is very small. The interaction of the solar wind with the earth's upper atmosphere during such a period is found to involve the formation of a bow shock. The penetration altitude of the shock-heated solar plasma is calculated to be about 700 km, and ionization rates above this level are estimated for a cascade ionization (electron avalanche) process to average 10 to the 9th power ions/sq cm/sec. The calculated ionization rates and the capacity of the solar wind to remove ionized helium (He4) from the upper atmosphere during geomagnetic dipole reversals are sufficient to yield a secular equilibrium over geologic time scales. The upward transport of helium from the lower atmosphere under these conditions is found to be adequate to sustain the proposed loss rate.

MALDI versus ESI: The Impact of the Ion Source on Peptide Identification.

PubMed

Nadler, Wiebke Maria; Waidelich, Dietmar; Kerner, Alexander; Hanke, Sabrina; Berg, Regina; Trumpp, Andreas; Rösli, Christoph

2017-03-03

For mass spectrometry-based proteomic analyses, electrospray ionization (ESI) and matrix-assisted laser desorption/ionization (MALDI) are the commonly used ionization techniques. To investigate the influence of the ion source on peptide detection in large-scale proteomics, an optimized GeLC/MS workflow was developed and applied either with ESI/MS or with MALDI/MS for the proteomic analysis of different human cell lines of pancreatic origin. Statistical analysis of the resulting data set with more than 72 000 peptides emphasized the complementary character of the two methods, as the percentage of peptides identified with both approaches was as low as 39%. Significant differences between the resulting peptide sets were observed with respect to amino acid composition, charge-related parameters, hydrophobicity, and modifications of the detected peptides and could be linked to factors governing the respective ion yields in ESI and MALDI.

Anomalous photo-ionization of 4d shell in medium-Z ionized atoms

NASA Astrophysics Data System (ADS)

Klapisch, M.; Busquet, M.

2013-09-01

Photoionization (PI) cross sections (PICS) are necessary for the simulation of astrophysical and ICF plasmas. In order to be used in plasma modeling, the PICS are usually fit to simple analytical formulas. We observed an unusual spectral shape of the PICS of the 4d shell of ionized Xe and other elements, computed with different codes: a local minimum occurs around twice the threshold energy. We explain this phenomenon as interference between the bound 4d wavefunction and the free electron wavefunction, which is similar to the Cooper minima for neutral atoms. Consequently, the usual fitting formulas, which consist of a combination of inverse powers of the frequency beyond threshold, may yield rates for PI and radiative recombination (RR) that are incorrect by orders of magnitude. A new fitting algorithm is proposed and is included in the latest version of HULLAC.v9.5.

Ionization-induced solvent migration in acetanilide-methanol clusters inferred from isomer-selective infrared spectroscopy.

PubMed

Weiler, Martin; Nakamura, Takashi; Sekiya, Hiroshi; Dopfer, Otto; Miyazaki, Mitsuhiko; Fujii, Masaaki

2012-12-07

We present the resonance-enhanced multiphoton ionization, infrared-ultraviolet hole burning (IR-UV HB), and IR dip spectra of the trans-acetanilide-methanol (AA-MeOH) cluster in the S(0), S(1), and cationic ground state (D(0)) in a supersonic jet. The IR-UV HB spectra demonstrate the co-existence of two isomers in S(0,1), in which MeOH binds either to the NH or the CO site of the peptide linkage in AA, denoted as AA(NH)-MeOH and AA(CO)-MeOH. When AA(CO)-MeOH is selectively ionized, its IR spectrum in D(0) is the same as that measured for AA(+) (NH)-MeOH. Thus, photoionization of AA(CO)-MeOH induces migration of MeOH from the CO to the NH site with 100% yield. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Discharge Oscillations in a Permanent Magnet Cylindrical Hall-Effect Thruster

NASA Technical Reports Server (NTRS)

Polzin, K. A.; Sooby, E. S.; Raitses, Y.; Merino, E.; Fisch, N. J.

2009-01-01

Measurements of the discharge current in a cylindrical Hall thruster are presented to quantify plasma oscillations and instabilities without introducing an intrusive probe into the plasma. The time-varying component of the discharge current is measured using a current monitor that possesses a wide frequency bandwidth and the signal is Fourier transformed to yield the frequency spectra present, allowing for the identification of plasma oscillations. The data show that the discharge current oscillations become generally greater in amplitude and complexity as the voltage is increased, and are reduced in severity with increasing flow rate. The breathing mode ionization instability is identified, with frequency as a function of discharge voltage not increasing with discharge voltage as has been observed in some traditional Hall thruster geometries, but instead following a scaling similar to a large-amplitude, nonlinear oscillation mode recently predicted in for annular Hall thrusters. A transition from lower amplitude oscillations to large relative fluctuations in the oscillating discharge current is observed at low flow rates and is suppressed as the mass flow rate is increased. A second set of peaks in the frequency spectra are observed at the highest propellant flow rate tested. Possible mechanisms that might give rise to these peaks include ionization instabilities and interactions between various oscillatory modes.

Performance parameters of a liquid filled ionization chamber array

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

Poppe, B.; Stelljes, T. S.; Looe, H. K.

2013-08-15

Purpose: In this work, the properties of the two-dimensional liquid filled ionization chamber array Octavius 1000SRS (PTW-Freiburg, Germany) for use in clinical photon-beam dosimetry are investigated.Methods: Measurements were carried out at an Elekta Synergy and Siemens Primus accelerator. For measurements of stability, linearity, and saturation effects of the 1000SRS array a Semiflex 31013 ionization chamber (PTW-Freiburg, Germany) was used as a reference. The effective point of measurement was determined by TPR measurements of the array in comparison with a Roos chamber (type 31004, PTW-Freiburg, Germany). The response of the array with varying field size and depth of measurement was evaluatedmore » using a Semiflex 31010 ionization chamber as a reference. Output factor measurements were carried out with a Semiflex 31010 ionization chamber, a diode (type 60012, PTW-Freiburg, Germany), and the detector array under investigation. The dose response function for a single detector of the array was determined by measuring 1 cm wide slit-beam dose profiles and comparing them against diode-measured profiles. Theoretical aspects of the low pass properties and of the sampling frequency of the detector array were evaluated. Dose profiles measured with the array and the diode detector were compared, and an intensity modulated radiation therapy (IMRT) field was verified using the Gamma-Index method and the visualization of line dose profiles.Results: The array showed a short and long term stability better than 0.1% and 0.2%, respectively. Fluctuations in linearity were found to be within ±0.2% for the vendor specified dose range. Saturation effects were found to be similar to those reported in other studies for liquid-filled ionization chambers. The detector's relative response varied with field size and depth of measurement, showing a small energy dependence accounting for maximum signal deviations of ±2.6% from the reference condition for the setup used. The σ-values of the Gaussian dose response function for a single detector of the array were found to be (0.72 ± 0.25) mm at 6 MV and (0.74 ± 0.25) mm at 15 MV and the corresponding low pass cutoff frequencies are 0.22 and 0.21 mm{sup −1}, respectively. For the inner 5 × 5 cm{sup 2} region and the outer 11 × 11 cm{sup 2} region of the array the Nyquist theorem is fulfilled for maximum sampling frequencies of 0.2 and 0.1 mm{sup −1}, respectively. An IMRT field verification with a Gamma-Index analysis yielded a passing rate of 95.2% for a 3 mm/3% criterion with a TPS calculation as reference.Conclusions: This study shows the applicability of the Octavius 1000SRS in modern dosimetry. Output factor and dose profile measurements illustrated the applicability of the array in small field and stereotactic dosimetry. The high spatial resolution ensures adequate measurements of dose profiles in regular and intensity modulated photon-beam fields.« less

Neon in ultrashort and intense x-rays from free electron lasers

NASA Astrophysics Data System (ADS)

Buth, Christian; Beerwerth, Randolf; Obaid, Razib; Berrah, Nora; Cederbaum, Lorenz S.; Fritzsche, Stephan

2018-03-01

We theoretically examine neon atoms in ultrashort and intense x-rays from free electron lasers and compare our results with data from experiments conducted at the Linac Coherent Light Source. For this purpose, we treat in detail the electronic structure in all possible nonrelativistic cationic configurations using a relativistic multiconfiguration approach. The interaction with the x-rays is described in rate-equation approximation. To understand the mechanisms of the interaction, a path analysis is devised which allows us to investigate what sequences of photoionization and decay processes lead to a specific configuration and with what probability. Thereby, we uncover a connection to the mathematics of graph theory and formal languages. In detail, we study the ion yields and find that plain rate equations do not provide a satisfactory description. We need to extend the rate equations for neon to incorporate double Auger decay of a K-shell vacancy and photoionization shake off for neutral neon. Shake off is included for valence and core ionization; the former has hitherto been overlooked but has important consequences for the ion yields from an x-ray energy below the core ionization threshold. Furthermore, we predict the photon yields from XUV and x-ray fluorescence these allow one insights into the configurations populated by the interaction with the x-rays. Finally, we discover that inaccuracies in those Auger decay widths employed in previous studies have only a minor influence on ion and photon yields.

Electron impact fragmentation of adenine: partial ionization cross sections for positive fragments

NASA Astrophysics Data System (ADS)

van der Burgt, Peter J. M.; Finnegan, Sinead; Eden, Samuel

2015-07-01

Using computer-controlled data acquisition we have measured mass spectra of positive ions for electron impact on adenine, with electron energies up to 100 eV. Ion yield curves for 50 ions have been obtained and normalized by comparing their sum to the average of calculated total ionization cross sections. Appearance energies have been determined for 37 ions; for 20 ions for the first time. All appearance energies are consistent with the fragmentation pathways identified in the literature. Second onset energies have been determined for 12 fragment ions (for 11 ions for the first time), indicating the occurrence of more than one fragmentation process e.g. for 39 u (C2HN+) and 70 u (C2H4N3+). Matching ion yield shapes (118-120 u, 107-108 u, 91-92 u, and 54-56 u) provide new evidence supporting closely related fragmentation pathways and are attributed to hydrogen rearrangement immediately preceding the fragmentation. We present the first measurement of the ion yield curve of the doubly charged parent ion (67.5 u), with an appearance energy of 23.5 ± 1.0 eV. Contribution to the Topical Issue "COST Action Nano-IBCT: Nano-scale Processes Behind Ion-Beam Cancer Therapy", edited by Andrey Solov'yov, Nigel Mason, Gustavo García, Eugene Surdutovich.

Sequential double photodetachment of He- in elliptically polarized laser fields

NASA Astrophysics Data System (ADS)

Génévriez, Matthieu; Dunseath, Kevin M.; Terao-Dunseath, Mariko; Urbain, Xavier

2018-02-01

Four-photon double detachment of the helium negative ion is investigated experimentally and theoretically for photon energies where the transient helium atom is in the 1 s 2 s 3S or 1 s 2 p P3o states, which subsequently ionize by absorption of three photons. Ionization is enhanced by intermediate resonances, giving rise to series of peaks in the He+ spectrum, which we study in detail. The He+ yield is measured in the wavelength ranges from 530 to 560 nm and from 685 to 730 nm and for various polarizations of the laser light. Double detachment is treated theoretically as a sequential process, within the framework of R -matrix theory for the first step and effective Hamiltonian theory for the second step. Experimental conditions are accurately modeled, and the measured and simulated yields are in good qualitative and, in some cases, quantitative agreement. Resonances in the double detachment spectra can be attributed to well-defined Rydberg states of the transient atom. The double detachment yield exhibits a strong dependence on the laser polarization which can be related to the magnetic quantum number of the intermediate atomic state. We also investigate the possibility of nonsequential double detachment with a two-color experiment but observe no evidence for it.

Copper fine-structure K-shell electron impact ionization cross sections for fast-electron diagnostic in laser-solid experiments

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

Palmeri, P., E-mail: patrick.palmeri@umons.ac.be; Quinet, P., E-mail: pascal.quinet@umons.ac.be; IPNAS, Université de Liège, B-4000 Liège

2015-03-15

The K-shell electron impact ionization (EII) cross section, along with the K-shell fluorescence yield, is one of the key atomic parameters for fast-electron diagnostic in laser-solid experiments through the K-shell emission cross section. In addition, copper is a material that has been often used in those experiments because it has a maximum total K-shell emission yield. Furthermore, in a campaign dedicated to the modeling of the K lines of astrophysical interest (Palmeri et al., 2012), the K-shell fluorescence yields for the K-vacancy fine-structure atomic levels of all the copper isonuclear ions have been calculated. In this study, the K-shell EII crossmore » sections connecting the ground and the metastable levels of the parent copper ions to the daughter ions K-vacancy levels considered in Palmeri et al. (2012) have been determined. The relativistic distorted-wave (DW) approximation implemented in the FAC atomic code has been used for the incident electron kinetic energies up to 10 times the K-shell threshold energies. Moreover, the resulting DW cross sections have been extrapolated at higher energies using the asymptotic form proposed by Davies et al. (2013)« less

Photoemission spectra and density functional theory calculations of 3d transition metal-aqua complexes (Ti-Cu) in aqueous solution.

PubMed

Yepes, Diana; Seidel, Robert; Winter, Bernd; Blumberger, Jochen; Jaque, Pablo

2014-06-19

Photoelectron spectroscopy measurements and density functional calculations are combined to determine the lowest electron binding energies of first-row transition-metal aqua ions, titanium through copper, with 3d(1) through 3d(9) electronic configurations, in their most common oxidation states. Vertical ionization energies are found to oscillate considerably between 6.76 and 9.65 eV for the dications and between 7.05 and 10.28 eV for the respective trivalent cations. The metal cations are modeled as [M(H2O)n](q+) clusters (q = 2, 3, and 4; n = 6 and 18) surrounded by continuum solvent. The performance of 10 exchange-correlation functionals, two GGAs, three MGGAs, two HGGAs and three HMGGAs, combined with the MDF10(ECP)/6-31+G(d,p) basis set is assessed for 11 M-O bond distances, 10 vertical ionization energies, 6 adiabatic ionization energies, and the associated reorganization free energies. We find that for divalent cations the HGGA and HMGGA functionals in combination with the 18 water model show the best agreement with experimental vertical ionization energies and geometries; for trivalent ions, the MGGA functionals perform best. The corresponding reorganization free energies (λo) of the oxidized ions are significantly underestimated with all DFT functionals and cluster models. This indicates that the structural reorganization of the solvation shell upon ionization is not adequately accounted for by the simple solvation models used, emphasizing the importance of extended sampling of thermally accessible solvation structures for an accurate computation of this quantity. The photoelectron spectroscopy measurements reported herein provide a comprehensive set of transition-metal redox energetic quantities for future electronic structure benchmarks.

Forming Rb(+) snowballs in the center of He nanodroplets.

PubMed

Theisen, Moritz; Lackner, Florian; Ernst, Wolfgang E

2010-12-07

Helium nanodroplets doped with rubidium atoms are ionized by applying a resonant two-step ionization scheme. Subsequent immersion of rubidium ions is observed in time-of-flight mass spectra. While alkali-metal atoms usually desorb from the surface of a helium nanodroplet upon electronic excitation, rubidium in its excited 5(2)P(1/2) state provides an exception from this rule (Auböck et al., Phys. Rev. Lett., 2008, 101, 35301). In our new experiment, Rb atoms are selectively excited either to the 5(2)P(1/2) or to the 5(2)P(3/2) state. From there they are ionized by a laser pulse. Time-of-flight mass spectra of the ionization products reveal that the intermediate population of the 5(2)P(1/2) state does not only make the ionization process Rb-monomer selective, but also gives rise to a very high yield of Rb(+)-He(N) complexes. Ions with masses of up to several thousand amu have been monitored, which can be explained by an immersion of the single Rb ion into the He nanodroplet, where most likely a snowball is formed in the center of the He nanodroplet. As the most stable position for an ion is in the center of a He nanodroplet, our results agree well with theory.

Uncatalyzed, Regioselective Oxidation of Saturated Hydrocarbons in an Ambient Corona Discharge.

PubMed

Ayrton, Stephen T; Jones, Rhys; Douce, David S; Morris, Mike R; Cooks, R Graham

2018-01-15

Atmospheric pressure chemical ionization (APCI) in air or in nitrogen with just traces of oxygen is shown to yield regioselective oxidation, dehydrogenation, and fragmentation of alkanes. Ozone is produced from ambient oxygen in situ and is responsible for the observed ion chemistry, which includes partial oxidation to ketones and C-C cleavage to give aldehydes. The mechanism of oxidation is explored and relationships between ionic species produced from individual alkanes are established. Unusually, dehydrogenation occurs by water loss. Competitive incorporation into the hydrocarbon chain of nitrogen versus oxygen as a mode of ionization is also demonstrated. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ion microscopy with resonant ionization mass spectrometry : time-of-flight depth profiling with improved isotopic precision.

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

Pellin, M. J.; Veryovkin, I. V.; Levine, J.

2010-01-01

There are four generally mutually exclusive requirements that plague many mass spectrometric measurements of trace constituents: (1) the small size (limited by the depth probed) of many interesting materials requires high useful yields to simply detect some trace elements, (2) the low concentrations of interesting elements require efficient discrimination from isobaric interferences, (3) it is often necessary to measure the depth distribution of elements with high surface and low bulk contributions, and (4) many applications require precise isotopic analysis. Resonant ionization mass spectrometry has made dramatic progress in addressing these difficulties over the past five years.

Mechanisms of Radiation Induced Effects in Carbon Nanotubes

DTIC Science & Technology

2016-10-01

the defect types created for both ionizing and non-ionizing particles under exposure to high total ionization and displacement damage doses. Carbon...and displacement damage doses. Additionally, the radiation effects on CNT carrier transport parameters (mobility, lifetime, conductivity) have been...thermal oxidation. 2. Radiation Testing of SWCNTs 2.1 Displacement Damage Dose Effects as a Function of SWCNT Electronic-Type Displacement damage does

Screening and identification of glyceollins and their metabolites by electrospray ionization tandem mass spectrometry with precursor ion scanning

USDA-ARS?s Scientific Manuscript database

A method has been developed for screening glyceollins and their metabolites based upon precursor ion scanning. Under higher-energy collision conditions, employing a triple quadrupole mass spectrometer in the negative ion mode, deprotonated glyceollin precursors yield a diagnostic radical product ion...

Technical Note: Impact of the geometry dependence of the ion chamber detector response function on a convolution-based method to address the volume averaging effect

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

Barraclough, Brendan; Lebron, Sharon; Li, Jonathan G.

2016-05-15

Purpose: To investigate the geometry dependence of the detector response function (DRF) of three commonly used scanning ionization chambers and its impact on a convolution-based method to address the volume averaging effect (VAE). Methods: A convolution-based approach has been proposed recently to address the ionization chamber VAE. It simulates the VAE in the treatment planning system (TPS) by iteratively convolving the calculated beam profiles with the DRF while optimizing the beam model. Since the convolved and the measured profiles are subject to the same VAE, the calculated profiles match the implicit “real” ones when the optimization converges. Three DRFs (Gaussian,more » Lorentzian, and parabolic function) were used for three ionization chambers (CC04, CC13, and SNC125c) in this study. Geometry dependent/independent DRFs were obtained by minimizing the difference between the ionization chamber-measured profiles and the diode-measured profiles convolved with the DRFs. These DRFs were used to obtain eighteen beam models for a commercial TPS. Accuracy of the beam models were evaluated by assessing the 20%–80% penumbra width difference (PWD) between the computed and diode-measured beam profiles. Results: The convolution-based approach was found to be effective for all three ionization chambers with significant improvement for all beam models. Up to 17% geometry dependence of the three DRFs was observed for the studied ionization chambers. With geometry dependent DRFs, the PWD was within 0.80 mm for the parabolic function and CC04 combination and within 0.50 mm for other combinations; with geometry independent DRFs, the PWD was within 1.00 mm for all cases. When using the Gaussian function as the DRF, accounting for geometry dependence led to marginal improvement (PWD < 0.20 mm) for CC04; the improvement ranged from 0.38 to 0.65 mm for CC13; for SNC125c, the improvement was slightly above 0.50 mm. Conclusions: Although all three DRFs were found adequate to represent the response of the studied ionization chambers, the Gaussian function was favored due to its superior overall performance. The geometry dependence of the DRFs can be significant for clinical applications involving small fields such as stereotactic radiotherapy.« less

Technical Note: Impact of the geometry dependence of the ion chamber detector response function on a convolution-based method to address the volume averaging effect.

PubMed

Barraclough, Brendan; Li, Jonathan G; Lebron, Sharon; Fan, Qiyong; Liu, Chihray; Yan, Guanghua

2016-05-01

To investigate the geometry dependence of the detector response function (DRF) of three commonly used scanning ionization chambers and its impact on a convolution-based method to address the volume averaging effect (VAE). A convolution-based approach has been proposed recently to address the ionization chamber VAE. It simulates the VAE in the treatment planning system (TPS) by iteratively convolving the calculated beam profiles with the DRF while optimizing the beam model. Since the convolved and the measured profiles are subject to the same VAE, the calculated profiles match the implicit "real" ones when the optimization converges. Three DRFs (Gaussian, Lorentzian, and parabolic function) were used for three ionization chambers (CC04, CC13, and SNC125c) in this study. Geometry dependent/independent DRFs were obtained by minimizing the difference between the ionization chamber-measured profiles and the diode-measured profiles convolved with the DRFs. These DRFs were used to obtain eighteen beam models for a commercial TPS. Accuracy of the beam models were evaluated by assessing the 20%-80% penumbra width difference (PWD) between the computed and diode-measured beam profiles. The convolution-based approach was found to be effective for all three ionization chambers with significant improvement for all beam models. Up to 17% geometry dependence of the three DRFs was observed for the studied ionization chambers. With geometry dependent DRFs, the PWD was within 0.80 mm for the parabolic function and CC04 combination and within 0.50 mm for other combinations; with geometry independent DRFs, the PWD was within 1.00 mm for all cases. When using the Gaussian function as the DRF, accounting for geometry dependence led to marginal improvement (PWD < 0.20 mm) for CC04; the improvement ranged from 0.38 to 0.65 mm for CC13; for SNC125c, the improvement was slightly above 0.50 mm. Although all three DRFs were found adequate to represent the response of the studied ionization chambers, the Gaussian function was favored due to its superior overall performance. The geometry dependence of the DRFs can be significant for clinical applications involving small fields such as stereotactic radiotherapy.

Radionuclide Ionization in Protoplanetary Disks: Calculations of Decay Product Radiative Transfer

NASA Astrophysics Data System (ADS)

Cleeves, L. Ilsedore; Adams, Fred C.; Bergin, Edwin A.; Visser, Ruud

2013-11-01

We present simple analytic solutions for the ionization rate ζSLR arising from the decay of short-lived radionuclides (SLRs) within protoplanetary disks. We solve the radiative transfer problem for the decay products within the disk, and thereby allow for the loss of radiation at low disk surface densities; energy loss becomes important outside R >~ 30 AU for typical disk masses Mg = 0.04 M ⊙. Previous studies of chemistry/physics in these disks have neglected the impact of ionization by SLRs, and often consider only cosmic rays (CRs), because of the high CR-rate present in the interstellar medium. However, recent work suggests that the flux of CRs present in the circumstellar environment could be substantially reduced by relatively modest stellar winds, resulting in severely modulated CR ionization rates, ζCR, equal to or substantially below that of SLRs (ζSLR <~ 10-18 s-1). We compute the net ionizing particle fluxes and corresponding ionization rates as a function of position within the disk for a variety of disk models. The resulting expressions are especially simple for the case of vertically Gaussian disks (frequently assumed in the literature). Finally, we provide a power-law fit to the ionization rate in the midplane as a function of gas disk surface density and time. Depending on location in the disk, the ionization rates by SLRs are typically in the range ζSLR ~ (1-10) × 10-19 s-1.

Thermophysics Characterization of Multiply Ionized Air Plasma Absorption of Laser Radiation

NASA Technical Reports Server (NTRS)

Wang, Ten-See; Rhodes, Robert; Turner, Jim (Technical Monitor)

2002-01-01

The impact of multiple ionization of air plasma on the inverse Bremsstrahlung absorption of laser radiation is investigated for air breathing laser propulsion. Thermochemical properties of multiply ionized air plasma species are computed for temperatures up to 200,000 deg K, using hydrogenic approximation of the electronic partition function; And those for neutral air molecules are also updated for temperatures up to 50,000 deg K, using available literature data. Three formulas for absorption are calculated and a general formula is recommended for multiple ionization absorption calculation. The plasma composition required for absorption calculation is obtained by increasing the degree of ionization sequentially, up to quadruple ionization, with a series of thermal equilibrium computations. The calculated second ionization absorption coefficient agrees reasonably well with that of available data. The importance of multiple ionization modeling is demonstrated with the finding that area under the quadruple ionization curve of absorption is found to be twice that of single ionization. The effort of this work is beneficial to the computational plasma aerodynamics modeling of laser lightcraft performance.

Formation and reactions of negative ions relevant to chemical ionization mass spectrometry. I. Cl mass spectra of organic compounds produced by F− reactions

PubMed Central

Tiernan, T. O.; Chang, C.; Cheng, C. C.

1980-01-01

A systematic study of the negative-ion chemical ionization mass spectra produced by the reaction of F− with a wide variety of organic compounds has been accomplished. A time-of-flight mass spectrometer fitted with a modified high pressure ion source was employed for these experiments. The F− reagent ion was generated from CF3H or NF3, typically at an ion source pressure of 100 μm. In pure NF3, F− is the major ion formed and constitutes more than 90% of the total ion intensity. While F− is also the major primary ion formed in pure CF3H, it undergoes rapid ion-molecule reactions at elevated source pressures, yielding (HF)nF− (n = 1−3) ions, which makes CF3H less suitable as a chemical ionization reagent gas. Among the organic compounds investigated were carboxylic acids, ketones, aldehydes, esters, alcohols, phenols, halides, nitriles, nitrobenzene, ethers, amines and hydrocarbons. An intense (M − 1)− ion was observed in the F− chemical ionization mass spectra of carboxylic acids, ketones, aldehydes and phenols. Alcohols yield only (M + F)− ions upon reaction with F−. A weaker (M + F)− ion was also detected in the F− chemical ionization spectra of carboxylic acids, aldehydes, ketones and nitriles. The F− chemical ionization mass spectra of esters, halides, nitriles, nitrobenzene and ethers are characterized primarily by the ions, RCOO−, X−, CN−, NO2−, and OR−, respectively. In addition, esters show a very weak (M − 1)− ion (except formates). In the F− chemical ionization spectra of some aliphatic alkanes and o-xylene, a very weak (M + F)− ion was observed. Amines and aliphatic alkenes exhibit only insignificant fragment ions under similar conditions, while aromatic hydrocarbons, such as benzene and toluene are not reactive at all with the F− ion. The mechanisms of the various reactions mentioned are discussed, and several experimental complications are noted. In still other studies, the effects of varying several experimental parameters, including source pressure, relative proportions of the reagent and analyte, and other ion source parameters, on the observed chemical ionization mass spectra were also investigated. In a mixture of NF3 and n-butanol, for example, the ratio of the intensities of the ions characteristic of the alcohol to that of the (HF)nF− ion was found to decrease with increasing sample pressure, with increasing NF3 pressure, and with increasing electron energy. No significant effects on the spectra were observed to result from variation of the source repeller field or the source temperature. The addition of argon to the source as a potential moderator did not alter the F− chemical ionization spectrum significantly, but the use of oxygen appears to inhibit formation of the (HF)nF− cluster ion. The advantages of using F− as a chemical ionization reagent are discussed, and comparisons are made with other reagent ions. PMID:7428746

Spectrophotometric and theoretical studies of the protonation of Allura Red AC and Ponceau 4R

NASA Astrophysics Data System (ADS)

Bevziuk, Kateryna; Chebotarev, Alexander; Snigur, Denys; Bazel, Yaroslav; Fizer, Maksym; Sidey, Vasyl

2017-09-01

The acid-base properties of Allura Red AC and Ponceau 4R azo dyes were investigated by spectrophotometric, potentiometric and tristimulus colourimetry methods. Ionization constants of the functional groups were also found in aqueous solutions of the dyes. It was discovered that the wavelength of the maximum light absorption of Allura Red AC and Ponceau 4R solutions does not change significantly over a wide pH range. As a result, spectrophotometric methods yield little information for assessing the acid-base properties of the dyes. It was shown with a help of the tristimulus colourimetry method that it is possible to determine the ionization constants of the functional groups of the dyes even when there is significant overlap of the absorption bands of the acid-base forms. The basic spectrophotometric characteristics of the main forms of Allura Red AC and Ponceau 4R in water and organic solvents were calculated. The molar absorbance coefficients of azo forms were shown to increase as the dielectric permittivity of the solvent increases. It was determined that in aqueous solution the dyes exist in the azo form over a wide range of acidity - pH 2-12 for Allura Red AC (λmax = 505 nm; ελ = 3.1·104 dm3 mol-1 cm-1) and 1-13 for Ponceau 4R (λmax = 510 nm; ελ = 1.7·10-4 dm3 mol-1 cm-1). The most probable protonation/deprotonation schemes were theoretically determined for Allura Red AC and Ponceau 4R using DFT calculations.

Low-energy electron stimulated desorption of neutrals from multilayers of SiCl4 on Si(111).

PubMed

Lane, Christopher D; Orlando, Thomas M

2006-04-28

The interaction of low-energy electrons with multilayers of SiCl(4) adsorbed on Si(111) leads to production and desorption of Cl((2)P(32)), Cl((2)P(12)), Si, and SiCl. Resonant structure in the yield versus incident electron energy (E(i)) between 6 and 12 eV was seen in all neutral channels and assigned to dissociative electron attachment (DEA), unimolecular decay of excited products produced via autodetachment and direct dissociation. These processes yield Cl((2)P(32)) and Cl((2)P(12)) with nonthermal kinetic energies of 425 and 608 meV, respectively. The Cl((2)P(12)) is produced solely at the vacuum surface interface, whereas the formation of Cl((2)P(32)) likely involves subsurface dissociation, off-normal trajectories, and collisions with neighbors. Structure in the Cl((2)P(32)) yield near 14 and 25 eV can originate from excitation of electrons in the 2e, 7t(2) and 6t(2), 6a(1) levels, respectively. Although the 14 eV feature was not present in the Cl((2)P(12)) yield, the broad 25 eV feature, which involves complex Auger filling of holes in the 6t(2) and 6a(1) levels of SiCl(4), is observed. Direct ionization, exciton decay, and DEA from secondary electron scattering all occur at E(i)>14 eV. Si and SiCl were detected via nonresonant ionization of SiCl(x) precursors that are produced via the same states and mechanisms that yield Cl. The Si retains the kinetic energy profile of the desorbed precursors.

Monte Carlo Simulations of Electron Energy-Loss Spectra with the Addition of Fine Structure from Density Functional Theory Calculations.

PubMed

Attarian Shandiz, Mohammad; Guinel, Maxime J-F; Ahmadi, Majid; Gauvin, Raynald

2016-02-01

A new approach is presented to introduce the fine structure of core-loss excitations into the electron energy-loss spectra of ionization edges by Monte Carlo simulations based on an optical oscillator model. The optical oscillator strength is refined using the calculated electron energy-loss near-edge structure by density functional theory calculations. This approach can predict the effects of multiple scattering and thickness on the fine structure of ionization edges. In addition, effects of the fitting range for background removal and the integration range under the ionization edge on signal-to-noise ratio are investigated.

Dense clumps of ionized gas near Pi Scorpii, as revealed by the fine-structure excitation of N II

NASA Technical Reports Server (NTRS)

Bertoldi, Frank; Jenkins, Edward B.

1992-01-01

The column density and the emission of the ionized gas along the line of sight toward the B1 V + B2 V binary star Pi Sco are measured on the basis of the fine-structure absorption lines of the ground state N II. It is found that the bulk of this ionized gas must be clumped on a length scale of 0.025 pc, which is far smaller than the observed size of the diffuse H II region surrounding Pi Sco of about 6 pc. The observed column density of S III toward Pi Sco yields an upper limit on the distance of the absorbing, clumped gas from the star of less than about 0.02 pc, assuming that both the N II and S III absorption arise from the same gas. The possibility that the ionized gas originates from a photoevaporating circumstellar disk directly surrounding Pi Sco is excluded, since such a disk would have an unusual size of order 0.025 pc and would have had to survive for the estimated age of Pi Sco of 5-8 Myr. The derived mean density of the clumped gas is of order 40/cu cm, so that the gas is at a pressure that far exceeds the mean pressure in the H II region. It is concluded that the ionized gas could originate from evaporation flows off a cluster of compact neutral objects that evaporate due to the ionizing radiation of Pi Sco.

First observation of HO˙ reactivity in water under high energy ions at elevated temperature.

PubMed

Balcerzyk, A; Boughattas, I; Pin, S; Balanzat, E; Baldacchino, G

2014-11-21

This communication reports the first observation of the formation of HO˙ produced under two different High energy ion beams, (18)O(8+) and (36)Ar(18+) having Linear Energy Transfers (LET) of 65 and 350 eV nm(-1) respectively, at temperatures up to 411 K. Both scavenging with various concentrations of SCN(-) and heavy-ion pulse radiolysis methods are used with an original temperature and pressure regulated optical cell. Deconvolution of kinetics is used to analyze the evolution of HO˙ track segment yields as a function of time and temperature. It takes care of involving the ionic strength effect and Arrhenius expression in the rate constants correction. The results show a fast decay of HO˙ yields in the 10(-10)-10(-8) s range which denotes an efficient reactivity of this species in the track structure of the ion beam. This effect is enhanced with the lowest LET of O(8+). Increasing the temperature also accelerates the decays for both ions. These observations are discussed in terms of temperature activation of reactions and the track structure exhibiting the formation of HO˙ in a "low LET" penumbra around the ionization tracks. HO˙ track segment yields at 100 ns, of 0.4 × 10(-7) and 0.6 × 10(-7) mol J(-1), respectively for 350 and 65 eV nm(-1), are not affected by temperature.

Development of a highly-sensitive Penning ionization electron spectrometer using the magnetic bottle effect

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

Ota, Masahiro; Ishiguro, Yuki; Nakajima, Yutaro

2016-02-01

This paper reports on a highly-sensitive retarding-type electron spectrometer for a continuous source of electrons, in which the electron collection efficiency is increased by utilizing the magnetic bottle effect. This study demonstrates an application to Penning ionization electron spectroscopy using collisional ionization with metastable He*(2{sup 3}S) atoms. Technical details and performances of the instrument are presented. This spectrometer can be used for studies of functional molecules and assemblies, and exterior electron densities are expected to be selectively observed by the Penning ionization.

Galaxy Properties and UV Escape Fractions during the Epoch of Reionization: Results from the Renaissance Simulations

NASA Astrophysics Data System (ADS)

Xu, Hao; Wise, John H.; Norman, Michael L.; Ahn, Kyungjin; O'Shea, Brian W.

2016-12-01

Cosmic reionization is thought to be primarily fueled by the first generations of galaxies. We examine their stellar and gaseous properties, focusing on the star formation rates and the escape of ionizing photons, as a function of halo mass, redshift, and environment using the full suite of the Renaissance Simulations with an eye to provide better inputs to global reionization simulations. This suite probes overdense, average, and underdense regions of the universe of several hundred comoving Mpc3, each yielding a sample of over 3000 halos in the mass range of 107-109.5 {M}⊙ at their final redshifts of 15, 12.5, and 8, respectively. In the process, we simulate the effects of radiative and supernova feedback from 5000 to 10,000 Population III stars in each simulation. We find that halos as small as 107 {M}⊙ are able to host bursty star formation due to metal-line cooling from earlier enrichment by massive Population III stars. Using our large sample, we find that the galaxy-halo occupation fraction drops from unity at virial masses above 108.5 {M}⊙ to ˜50% at 108 {M}⊙ and ˜10% at 107 {M}⊙ , quite independent of redshift and region. Their average ionizing escape fraction is ˜5% in the mass range of 108-109 {M}⊙ and increases with decreasing halo mass below this range, reaching 40%-60% at 107 {M}⊙ . Interestingly, we find that the escape fraction varies between 10%-20% in halos with virial masses of ˜3 × 109 {M}⊙ . Taken together, our results confirm the importance of the smallest galaxies as sources of ionizing radiation contributing to the reionization of the universe.

Donor ionization in size controlled silicon nanocrystals: The transition from defect passivation to free electron generation

NASA Astrophysics Data System (ADS)

Crowe, I. F.; Papachristodoulou, N.; Halsall, M. P.; Hylton, N. P.; Hulko, O.; Knights, A. P.; Yang, P.; Gwilliam, R. M.; Shah, M.; Kenyon, A. J.

2013-01-01

We studied the photoluminescence spectra of silicon and phosphorus co-implanted silica thin films on (100) silicon substrates as a function of isothermal annealing time. The rapid phase segregation, formation, and growth dynamics of intrinsic silicon nanocrystals are observed, in the first 600 s of rapid thermal processing, using dark field mode X-TEM. For short annealing times, when the nanocrystal size distribution exhibits a relatively small mean diameter, formation in the presence of phosphorus yields an increase in the luminescence intensity and a blue shift in the emission peak compared with intrinsic nanocrystals. As the mean size increases with annealing time, this enhancement rapidly diminishes and the peak energy shifts further to the red than the intrinsic nanocrystals. These results indicate the existence of competing pathways for the donor electron, which depends strongly on the nanocrystal size. In samples containing a large density of relatively small nanocrystals, the tendency of phosphorus to accumulate at the nanocrystal-oxide interface means that ionization results in a passivation of dangling bond (Pb-centre) type defects, through a charge compensation mechanism. As the size distribution evolves with isothermal annealing, the density of large nanocrystals increases at the expense of smaller nanocrystals, through an Ostwald ripening mechanism, and the majority of phosphorus atoms occupy substitutional lattice sites within the nanocrystals. As a consequence of the smaller band-gap, ionization of phosphorus donors at these sites increases the free carrier concentration and opens up an efficient, non-radiative de-excitation route for photo-generated electrons via Auger recombination. This effect is exacerbated by an enhanced diffusion in phosphorus doped glasses, which accelerates silicon nanocrystal growth.

Quantitative measurement of the chemical composition of geological standards with a miniature laser ablation/ionization mass spectrometer designed for in situ application in space research

NASA Astrophysics Data System (ADS)

Neuland, M. B.; Grimaudo, V.; Mezger, K.; Moreno-García, P.; Riedo, A.; Tulej, M.; Wurz, P.

2016-03-01

A key interest of planetary space missions is the quantitative determination of the chemical composition of the planetary surface material. The chemical composition of surface material (minerals, rocks, soils) yields fundamental information that can be used to answer key scientific questions about the formation and evolution of the planetary body in particular and the Solar System in general. We present a miniature time-of-flight type laser ablation/ionization mass spectrometer (LMS) and demonstrate its capability in measuring the elemental and mineralogical composition of planetary surface samples quantitatively by using a femtosecond laser for ablation/ionization. The small size and weight of the LMS make it a remarkable tool for in situ chemical composition measurements in space research, convenient for operation on a lander or rover exploring a planetary surface. In the laboratory, we measured the chemical composition of four geological standard reference samples USGS AGV-2 Andesite, USGS SCo-l Cody Shale, NIST 97b Flint Clay and USGS QLO-1 Quartz Latite with LMS. These standard samples are used to determine the sensitivity factors of the instrument. One important result is that all sensitivity factors are close to 1. Additionally, it is observed that the sensitivity factor of an element depends on its electron configuration, hence on the electron work function and the elemental group in agreement with existing theory. Furthermore, the conformity of the sensitivity factors is supported by mineralogical analyses of the USGS SCo-l and the NIST 97b samples. With the four different reference samples, the consistency of the calibration factors can be demonstrated, which constitutes the fundamental basis for a standard-less measurement-technique for in situ quantitative chemical composition measurements on planetary surface.

THERMODYNAMICS AND CHARGING OF INTERSTELLAR IRON NANOPARTICLES

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

Hensley, Brandon S.; Draine, B. T., E-mail: brandon.s.hensley@jpl.nasa.gov

Interstellar iron in the form of metallic iron nanoparticles may constitute a component of the interstellar dust. We compute the stability of iron nanoparticles to sublimation in the interstellar radiation field, finding that iron clusters can persist down to a radius of ≃4.5 Å, and perhaps smaller. We employ laboratory data on small iron clusters to compute the photoelectric yields as a function of grain size and the resulting grain charge distribution in various interstellar environments, finding that iron nanoparticles can acquire negative charges, particularly in regions with high gas temperatures and ionization fractions. If ≳10% of the interstellar ironmore » is in the form of ultrasmall iron clusters, the photoelectric heating rate from dust may be increased by up to tens of percent relative to dust models with only carbonaceous and silicate grains.« less

X-ray source characterization of aluminum X-pinch plasmas driven by the 0. 5 TW LION accelerator

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

Qi, N.; Hammer, D.A.; Kalantar, D.H.

1989-12-01

Recent experiments at Cornell have been performed to investigate X-pinch plasmas as intense x-ray sources which might be used to pump resonant photoexcitation lasers. Crossed Al wires have been driven by up to 600 kA current for 40 ns. High density bright spots are observed at the crossing point(s). Various diagnostics were used to characterize the X-pinch plasmas as a function of initial mass loading for several specific wire configurations. The optimum mass loading for different ionization stages of Al, and the total x-ray energy yields, which are on the order of hundreds of Joules, were examined. Estimates of plasmamore » density, {similar to}10{sup 20} cm{sup {minus}3}, and temperature, about 400 eV, were obtained.« less

Microwave Assisted Synthesis, Physicochemical, Photophysical, Single Crystal X-ray and DFT Studies of Novel Push-Pull Chromophores.

PubMed

Khan, Salman A; Asiri, Abdullah M; Basisi, Hadi Mussa; Arshad, Muhammad Nadeem; Sharma, Kamlesh

2015-11-01

Two push-pull chromophores were synthesized by knoevenagel condensation under microwave irradiation. The structure of synthesized chromophores were established by spectroscopic (FT-IR, (1)H NMR, (13)C NMR, EI-MS) and elemental analysis. Structure of the chromophores was further conformed by X-ray crystallographic. UV-Vis and fluorescence spectroscopy measurements provided that chromophores were good absorbent and fluorescent properties. Fluorescence polarity studies demonstrated that chromophores were sensitive to the polarity of the microenvironment provided by different solvents. Physicochemical parameters, including singlet absorption, extinction coefficient, stokes shift, oscillator strength, dipole moment and flurescence quantum yield were investigated in order to explore the analytical potential of the synthesized chromophores. In addition, the total energy, frontier molecular orbitals, hardness, electron affinity, ionization energy, electrostatic potential map were also studied computationally by using density functional theoretical method.

Convergent close coupling versus the generalized Sturmian function approach: Wave-function analysis

NASA Astrophysics Data System (ADS)

Ambrosio, M.; Mitnik, D. M.; Gasaneo, G.; Randazzo, J. M.; Kadyrov, A. S.; Fursa, D. V.; Bray, I.

2015-11-01

We compare the physical information contained in the Temkin-Poet (TP) scattering wave function representing electron-impact ionization of hydrogen, calculated by the convergent close-coupling (CCC) and generalized Sturmian function (GSF) methodologies. The idea is to show that the ionization cross section can be extracted from the wave functions themselves. Using two different procedures based on hyperspherical Sturmian functions we show that the transition amplitudes contained in both GSF and CCC scattering functions lead to similar single-differential cross sections. The single-continuum channels were also a subject of the present studies, and we show that the elastic and excitation amplitudes are essentially the same as well.

Theory of electron-impact ionization of atoms

NASA Astrophysics Data System (ADS)

Kadyrov, A. S.; Mukhamedzhanov, A. M.; Stelbovics, A. T.; Bray, I.

2004-12-01

The existing formulations of electron-impact ionization of a hydrogenic target suffer from a number of formal problems including an ambiguous and phase-divergent definition of the ionization amplitude. An alternative formulation of the theory is given. An integral representation for the ionization amplitude which is free of ambiguity and divergence problems is derived and is shown to have four alternative, but equivalent, forms well suited for practical calculations. The extension to amplitudes of all possible scattering processes taking place in an arbitrary three-body system follows. A well-defined conventional post form of the breakup amplitude valid for arbitrary potentials including the long-range Coulomb interaction is given. Practical approaches are based on partial-wave expansions, so the formulation is also recast in terms of partial waves and partial-wave expansions of the asymptotic wave functions are presented. In particular, expansions of the asymptotic forms of the total scattering wave function, developed from both the initial and the final state, for electron-impact ionization of hydrogen are given. Finally, the utility of the present formulation is demonstrated on some well-known model problems.

Planarizing cytosine: The S1 state structure, vibrations, and nonradiative dynamics of jet-cooled 5,6-trimethylenecytosine

NASA Astrophysics Data System (ADS)

Trachsel, Maria A.; Lobsiger, Simon; Schär, Tobias; Blancafort, Lluís; Leutwyler, Samuel

2017-06-01

We measure the S0 → S1 spectrum and time-resolved S1 state nonradiative dynamics of the "clamped" cytosine derivative 5,6-trimethylenecytosine (TMCyt) in a supersonic jet, using two-color resonant two-photon ionization (R2PI), UV/UV holeburning, and ns time-resolved pump/delayed ionization. The experiments are complemented with spin-component scaled second-order approximate coupled cluster (SCS-CC2), time-dependent density functional theory, and multi-state second-order perturbation-theory (MS-CASPT2) ab initio calculations. While the R2PI spectrum of cytosine breaks off ˜500 cm-1 above its 000 band, that of TMCyt extends up to +4400 cm-1 higher, with over a hundred resolved vibronic bands. Thus, clamping the cytosine C5-C6 bond allows us to explore the S1 state vibrations and S0 → S1 geometry changes in detail. The TMCyt S1 state out-of-plane vibrations ν1', ν3', and ν5' lie below 420 cm-1, and the in-plane ν11', ν12', and ν23' vibrational fundamentals appear at 450, 470, and 944 cm-1. S0 → S1 vibronic simulations based on SCS-CC2 calculations agree well with experiment if the calculated ν1', ν3', and ν5' frequencies are reduced by a factor of 2-3. MS-CASPT2 calculations predict that the ethylene-type S1 ⇝ S0 conical intersection (CI) increases from +366 cm-1 in cytosine to >6000 cm-1 in TMCyt, explaining the long lifetime and extended S0 → S1 spectrum. The lowest-energy S1 ⇝ S0 CI of TMCyt is the "amino out-of-plane" (OPX) intersection, calculated at +4190 cm-1. The experimental S1 ⇝ S0 internal conversion rate constant at the S1(v'=0 ) level is kI C=0.98 -2.2 ṡ1 08 s-1, which is ˜10 times smaller than in 1-methylcytosine and cytosine. The S1(v'=0 ) level relaxes into the T1(3π π *) state by intersystem crossing with kI S C=0.41 -1.6 ṡ1 08 s-1. The T1 state energy is measured to lie 24 580 ±560 cm-1 above the S0 state. The S1(v'=0 ) lifetime is τ =2.9 ns, resulting in an estimated fluorescence quantum yield of Φf l=24 %. Intense two-color R2PI spectra of the TMCyt amino-enol tautomers appear above 36 000 cm-1. A sharp S1 ionization threshold is observed for amino-keto TMCyt, yielding an adiabatic ionization energy of 8.114 ±0.002 eV.

Resonance ionization laser ion sources for on-line isotope separators (invited).

PubMed

Marsh, B A

2014-02-01

A Resonance Ionization Laser Ion Source (RILIS) is today considered an essential component of the majority of Isotope Separator On Line (ISOL) facilities; there are seven laser ion sources currently operational at ISOL facilities worldwide and several more are under development. The ionization mechanism is a highly element selective multi-step resonance photo-absorption process that requires a specifically tailored laser configuration for each chemical element. For some isotopes, isomer selective ionization may even be achieved by exploiting the differences in hyperfine structures of an atomic transition for different nuclear spin states. For many radioactive ion beam experiments, laser resonance ionization is the only means of achieving an acceptable level of beam purity without compromising isotope yield. Furthermore, by performing element selection at the location of the ion source, the propagation of unwanted radioactivity downstream of the target assembly is reduced. Whilst advances in laser technology have improved the performance and reliability of laser ion sources and broadened the range of suitable commercially available laser systems, many recent developments have focused rather on the laser/atom interaction region in the quest for increased selectivity and/or improved spectral resolution. Much of the progress in this area has been achieved by decoupling the laser ionization from competing ionization processes through the use of a laser/atom interaction region that is physically separated from the target chamber. A new application of gas catcher laser ion source technology promises to expand the capabilities of projectile fragmentation facilities through the conversion of otherwise discarded reaction fragments into high-purity low-energy ion beams. A summary of recent RILIS developments and the current status of laser ion sources worldwide is presented.

Kinetic Monte Carlo simulations of excitation density dependent scintillation in CsI and CsI(Tl)

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

Wang, Zhiguo; Williams, Richard; Grim, Joel

2013-08-15

Nonlinear quenching of electron-hole pairs in the denser regions of ionization tracks created by γ-ray and high-energy electrons is a likely cause of the light yield nonproportionality of many inorganic scintillators. Therefore, kinetic Monte Carlo (KMC) simulations were carried out to investigate the scintillation properties of pure and thallium-doped CsI as a function of electron-hole pair density. The availability of recent experimental data on the excitation density dependence of the light yield of CsI following ultraviolet excitation allowed for an improved parameterization of the interactions between self-trapped excitons (STE) in the KMC model via dipole-dipole Förster transfer. The KMC simulationsmore » reveal that nonlinear quenching occurs very rapidly (within a few picoseconds) in the early stages of the scintillation process. In addition, the simulations predict that the concentration of thallium activators can affect the extent of nonlinear quenching as it has a direct influence on the STE density through STE dissociation and electron scavenging. This improved model will enable more realistic simulations of the nonproportional γ-ray and electron response of inorganic scintillators.« less

Long-range-corrected Rung 3.5 density functional approximations

NASA Astrophysics Data System (ADS)

Janesko, Benjamin G.; Proynov, Emil; Scalmani, Giovanni; Frisch, Michael J.

2018-03-01

Rung 3.5 functionals are a new class of approximations for density functional theory. They provide a flexible intermediate between exact (Hartree-Fock, HF) exchange and semilocal approximations for exchange. Existing Rung 3.5 functionals inherit semilocal functionals' limitations in atomic cores and density tails. Here we address those limitations using range-separated admixture of HF exchange. We present three new functionals. LRC-ωΠLDA combines long-range HF exchange with short-range Rung 3.5 ΠLDA exchange. SLC-ΠLDA combines short- and long-range HF exchange with middle-range ΠLDA exchange. LRC-ωΠLDA-AC incorporates a combination of HF, semilocal, and Rung 3.5 exchange in the short range, based on an adiabatic connection. We test these in a new Rung 3.5 implementation including up to analytic fourth derivatives. LRC-ωΠLDA and SLC-ΠLDA improve atomization energies and reaction barriers by a factor of 8 compared to the full-range ΠLDA. LRC-ωΠLDA-AC brings further improvement approaching the accuracy of standard long-range corrected schemes LC-ωPBE and SLC-PBE. The new functionals yield highest occupied orbital energies closer to experimental ionization potentials and describe correctly the weak charge-transfer complex of ethylene and dichlorine and the hole-spin distribution created by an Al defect in quartz. This study provides a framework for more flexible range-separated Rung 3.5 approximations.

The duration of reionization constrains the ionizing sources

NASA Astrophysics Data System (ADS)

Sharma, Mahavir; Theuns, Tom; Frenk, Carlos

2018-06-01

We investigate how the nature of the galaxies that reionized the Universe affects the duration of reionization. We contrast two sets of models: one in which galaxies on the faint side of the luminosity function dominate the ionizing emissivity, and a second in which the galaxies on the bright side of the luminosity function dominate. The faint end of the luminosity function evolves slowly, therefore the transition from mostly neutral to mostly ionized state takes a much longer time in the first set of models compared to the second. Existing observational constraints on the duration of this transition are relatively weak, but taken at face value prefer the model in which galaxies on the bright side play a major role. Measurements of the kinetic Sunyaev-Zeldovich effect in the cosmic microwave background from the epoch of reionization also point in the same direction.

Noncontact bimolecular photoionization followed by radical-ions separation and their geminate recombination assisted by coherent HFI induced spin-conversion.

PubMed

Dodin, Dmitry V; Ivanov, Anatoly I; Burshtein, Anatoly I

2008-02-07

The Hamiltonian description of the spin-conversion induced by a hyperfine interaction (HFI) in photogenerated radical-ion pairs is substituted for the rate (incoherent) description of the same conversion provided by the widely used earlier elementary spin model. The quantum yields of the free ions as well as the singlet and triplet products of geminate recombination are calculated using distant dependent ionization and recombination rates, instead of their contact analogs. Invoking the simplest models of these rates, we demonstrate with the example of a spin-less system that the diffusional acceleration of radical-ion pair recombination at lower viscosity gives way to its diffusional deceleration (Angulo effect), accomplished with a kinetic plateau inherent with the primitive exponential model. Qualitatively the same behavior is found in real systems, assuming both ionization and recombination is carried out by the Marcus electron-transfer rates. Neglecting the Coulomb interaction between solvated ions, the efficiencies of radical-ion pair recombination to the singlet and triplet products are well fitted to the available experimental data. The magnetic field dependence of these yields is specified.

3D printing of graphene-doped target for "matrix-free" laser desorption/ionization mass spectrometry.

PubMed

Wang, Dingyi; Huang, Xiu; Li, Jie; He, Bin; Liu, Qian; Hu, Ligang; Jiang, Guibin

2018-03-13

We report a graphene-doped resin target fabricated via a 3D printing technique for laser desorption/ionization mass spectrometry analysis. The graphene doped in the target acts as an inherent laser absorber and ionization promoter, thus permitting the direct analysis of samples without adding matrix. This work reveals a new strategy for easy designing and fabrication of functional mass spectrometry devices.

Basic Mechanisms of Radiation Effects in Electronic Materials and Devices

DTIC Science & Technology

1987-09-01

power as function of particle energy for electrons and protons Incident on silic,,n...8217-Mev 0000 Neutrons0 0 Fluenoe n/oma e 1-MeV equivalent fluenos n/orm DlSlLAOUMllW Ionizing radltlon O Stopping power (linear energy MeV/(g/om...from the interaction of radiation energy that goes Into ionization Is given by the stop- with electronic materials are Ionization (primarily ping power

Liquid Sampling-Atmospheric Pressure Glow Discharge (LS-APGD) Ionization Source for Elemental Mass Spectrometry: Preliminary Parametric Evaluation and Figures of Merit

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

Quarles, C. Derrick; Carado, Anthony J.; Barinaga, Charles J.

2012-01-01

A new, low power ionization source for the elemental analysis of aqueous solutions has recently been described. The liquid sampling-atmospheric pressure glow discharge (LS-APGD) source operates at relatively low currents (<20 mA) and solution flow rates (<50 μL min-1), yielding a relatively simple alternative for atomic mass spectrometry applications. The LS-APGD has been interfaced to what is otherwise an organic, LC-MS mass analyzer, the Thermo Scientific Exactive Orbitrap without any modifications; other than removing the electrospray ionization (ESI) source supplied with that instrument. A glow discharge is initiated between the surface of the test solution exiting a glass capillary andmore » a metallic counter electrode mounted at a 90° angle and separated by a distance of ~5 mm. As with any plasma-based ionization source, there are key discharge operation and ion sampling parameters that affect the intensity and composition of the derived mass spectra; including signal-to-background ratios. We describe here a preliminary parametric evaluation of the roles of discharge current, solution flow rate, argon sheath gas flow rate, and ion sampling distance as they apply on this mass analyzer system. A cursive evaluation of potential matrix effects due to the presence of easily ionized elements (EIEs) indicate that sodium concentrations of up to 500 μg mL-1 generally cause suppressions of less than 50%, dependant upon the analyte species. Based on the results of this series of studies, preliminary limits of detection (LOD) have been established through the generation of calibration functions. Whilst solution-based concentrations LOD levels of 0.02 – 2 μg mL-1 3 are not impressive on the surface, the fact that they are determined via discrete 5 μL injections leads to mass-based detection limits at picogram to singlenanogram levels. The overhead costs associated with source operation (10 W d.c. power, solution flow rates of <50 μL min-1, and gas flow rates <10 mL min-1) are very attractive. While further optimization in the source design is suggested here, it is believed that the LS-APGD ion source may present a practical alternative to inductively-coupled plasma (ICP) sources typically employed in elemental mass spectrometry.« less

Attosecond Coherent Control of the Photo-Dissociation of Oxygen Molecules

NASA Astrophysics Data System (ADS)

Sturm, Felix; Ray, Dipanwita; Wright, Travis; Shivaram, Niranjan; Bocharova, Irina; Slaughter, Daniel; Ranitovic, Predrag; Belkacem, Ali; Weber, Thorsten

2016-05-01

Attosecond Coherent Control has emerged in recent years as a technique to manipulate the absorption and ionization in atoms as well as the dissociation of molecules on an attosecond time scale. Single attosecond pulses and attosecond pulse trains (APTs) can coherently excite multiple electronic states. The electronic and nuclear wave packets can then be coupled with a second pulse forming multiple interfering quantum pathways. We have built a high flux extreme ultraviolet (XUV) light source delivering APTs based on HHG that allows to selectively excite neutral and ion states in molecules. Our beamline provides spectral selectivity and attosecond interferometric control of the pulses. In the study presented here, we use APTs, generated by High Harmonic Generation in a high flux extreme ultraviolet light source, to ionize highly excited states of oxygen molecules. We identify the ionization/dissociation pathways revealing vibrational structure with ultra-high resolution ion 3D-momentum imaging spectroscopy. Furthermore, we introduce a delay between IR pulses and XUV/IR pulses to constructively or destructively interfere the ionization and dissociation pathways, thus, enabling the manipulation of both the O2+and the O+ ion yields with attosecond precision. Supported by DOE under Contract No. DE-AC02-05CH11231.

The Suzaku Observation of NGC 3516: Complex Absorption and the Broad and Narrow Fe K Lines

NASA Technical Reports Server (NTRS)

Markowitz, Alex; Reeves, James N.; Miniutti, Giovanni; Serlemitsos, Peter; Kunieda, Hideyo; Taqoob, Tahir; Fabian, Andrew C.; Fukazawa, Yasushi; Mushotzky, Richard; Okajima, Takashi;

Nanoengineering of strong field processes in solids

NASA Astrophysics Data System (ADS)

Almalki, S.; Parks, A. M.; Brabec, T.; McDonald, C. R.

2018-04-01

We present a theoretical investigation of the effect of quantum confinement on high harmonic generation in semiconductor materials by systematically varying the confinement width along one or two directions transverse to the laser polarization. Our analysis shows a growth in high harmonic efficiency concurrent with a reduction of ionization. This decrease in ionization comes as a consequence of an increased band gap resulting from the confinement. The increase in harmonic efficiency results from a restriction of wave packet spreading, leading to greater recollision probability. Consequently, nanoengineering of one and two-dimensional nanosystems may prove to be a viable means to increase harmonic yield and photon energy in semiconductor materials driven by intense laser fields.

Ionization tube simmer current circuit

DOEpatents

Steinkraus, R.F. Jr.

1994-12-13

A highly efficient flash lamp simmer current circuit utilizes a fifty percent duty cycle square wave pulse generator to pass a current over a current limiting inductor to a full wave rectifier. The DC output of the rectifier is then passed over a voltage smoothing capacitor through a reverse current blocking diode to a flash lamp tube to sustain ionization in the tube between discharges via a small simmer current. An alternate embodiment of the circuit combines the pulse generator and inductor in the form of an FET off line square wave generator with an impedance limited step up output transformer which is then applied to the full wave rectifier as before to yield a similar simmer current. 6 figures.

A feasibility study of ion implantation techniques for mass spectrometer calibration

NASA Technical Reports Server (NTRS)

Koslin, M. E.; Krycuk, G. A.; Schatz, J. G., Jr.; White, F. A.; Wood, G. M.

1978-01-01

An experimental study was undertaken to examine the feasibility of using ion-implanted filaments doped with either an alkali metal or noble gas for in situ recalibration of onboard mass spectrometers during extended space missions. Implants of rubidium and krypton in rhenium ribbon filaments were subsequently tested in a bakeable 60 deg sector mass spectrometer operating in the static mode. Surface ionization and electron impact ion sources were both used, each yielding satisfactory results. The metallic implant with subsequent ionization provided a means of mass scale calibration and determination of system operating parameters, whereas the noble gas thermally desorbed into the system was more suited for partial pressure and sensitivity determinations.

On determining absolute entropy without quantum theory or the third law of thermodynamics

NASA Astrophysics Data System (ADS)

Steane, Andrew M.

2016-04-01

We employ classical thermodynamics to gain information about absolute entropy, without recourse to statistical methods, quantum mechanics or the third law of thermodynamics. The Gibbs-Duhem equation yields various simple methods to determine the absolute entropy of a fluid. We also study the entropy of an ideal gas and the ionization of a plasma in thermal equilibrium. A single measurement of the degree of ionization can be used to determine an unknown constant in the entropy equation, and thus determine the absolute entropy of a gas. It follows from all these examples that the value of entropy at absolute zero temperature does not need to be assigned by postulate, but can be deduced empirically.

Ionization tube simmer current circuit

DOEpatents

Steinkraus, Jr., Robert F.

1994-01-01

A highly efficient flash lamp simmer current circuit utilizes a fifty percent duty cycle square wave pulse generator to pass a current over a current limiting inductor to a full wave rectifier. The DC output of the rectifier is then passed over a voltage smoothing capacitor through a reverse current blocking diode to a flash lamp tube to sustain ionization in the tube between discharges via a small simmer current. An alternate embodiment of the circuit combines the pulse generator and inductor in the form of an FET off line square wave generator with an impedance limited step up output transformer which is then applied to the full wave rectifier as before to yield a similar simmer current.

Structural characterization of saturated branched chain fatty acid methyl esters by collisional dissociation of molecular ions generated by electron ionization.

PubMed

Ran-Ressler, Rinat R; Lawrence, Peter; Brenna, J Thomas

2012-01-01

Saturated branched chain fatty acids (BCFA) are present as complex mixtures in numerous biological samples. The traditional method for structure elucidation, electron ionization (EI) mass spectrometry, sometimes does not unambiguously enable assignment of branching in isomeric BCFA. Zirrolli and Murphy (Zirrolli , J. A. , and R. A. Murphy. 1993. Low-energy tandem mass spectrometry of the molecular ion derived from fatty acid methyl esters: a novel method for analysis of branched-chain fatty acids. J. Am. Soc. Mass Spectrom. 4: 223-229.) showed that the molecular ions of four BCFA methyl ester (BCFAME) yield highly characteristic fragments upon collisional dissociation using a triple quadrupole instrument. Here, we confirm and extend these results by analysis using a tabletop 3-D ion trap for activated molecular ion EI-MS/MS to 30 BCFAME. iso-BCFAME produces a prominent ion (30-100% of base peak) for [M-43] (M-C₃H₇), corresponding to the terminal isopropyl moiety in the original iso-BCFAME. Anteiso-FAME yield prominent ions (20-100% of base peak) corresponding to losses on both side of the methyl branch, [M-29] and [M-57], and tend to produce more prominent m/z 115 peaks corresponding to a cyclization product around the ester. Dimethyl and tetramethyl FAME, with branches separated by at least one methylene group, yield fragment on both sides of the sites of methyl branches that are more than 6 C away from the carboxyl carbon. EI-MS/MS yields uniquely specific ions that enable highly confident structural identification and quantification of BCFAME.

Using luminescent materials as the active element for radiation sensors

NASA Astrophysics Data System (ADS)

Hollerman, William A.; Fontenot, Ross S.; Williams, Stephen; Miller, John

2016-05-01

Ionizing radiation poses a significant challenge for Earth-based defense applications as well as human and/or robotic space missions. Practical sensors based on luminescence will depend heavily upon research investigating the resistance of these materials to ionizing radiation and the ability to anneal or self-heal from damage caused by such radiation. In 1951, Birks and Black showed experimentally that the luminescent efficiency of anthracene bombarded by alphas varies with total fluence (N) as (I/I0) = 1/(1 + AN), where I is the luminescence yield, I0 is the initial yield, and A is a constant. The half brightness (N1/2) is defined as the fluence that reduce the emission light yield to half and is equal to is the inverse of A. Broser and Kallmann developed a similar relationship to the Birks and Black equation for inorganic phosphors irradiated using alpha particles. From 1990 to the present, we found that the Birks and Black relation describes the reduction in light emission yield for every tested luminescent material except lead phosphate glass due to proton irradiation. These results indicate that radiation produced quenching centers compete with emission for absorbed energy. The purpose of this paper is to present results from research completed in this area over the last few years. Particular emphasis will be placed on recent measurements made on new materials such as europium tetrakis dibenzoylmethide triethylammonium (EuD4TEA). Results have shown that EuD4TEA with its relatively small N1/2 might be a good candidate for use as a personal proton fluence sensor.

Characterization of direct-current atmospheric-pressure discharges useful for ambient desorption/ionization mass spectrometry.

PubMed

Shelley, Jacob T; Wiley, Joshua S; Chan, George C Y; Schilling, Gregory D; Ray, Steven J; Hieftje, Gary M

2009-05-01

Two relatively new ambient ionization sources, direct analysis in real time (DART) and the flowing atmospheric-pressure afterglow (FAPA), use direct current, atmospheric-pressure discharges to produce reagent ions for the direct ionization of a sample. Although at a first glance these two sources appear similar, a fundamental study reveals otherwise. Specifically, DART was found to operate with a corona-to-glow transition (C-G) discharge whereas the FAPA was found to operate with a glow-to-arc transition (G-A) discharge. The characteristics of both discharges were evaluated on the basis of four factors: reagent-ion production, response to a model analyte (ferrocene), infrared (IR) thermography of the gas used for desorption and ionization, and spatial emission characteristics. The G-A discharge produced a greater abundance and a wider variety of reagent ions than the C-G discharge. In addition, the discharges yielded different adducts and signal strengths for ferrocene. It was also found that the gas exiting the discharge chamber reached a maximum of 235 degrees C and 55 degrees C for the G-A and C-G discharges, respectively. Finally, spatially resolved emission maps of both discharges showed clear differences for N(2)(+) and O(I). These findings demonstrate that the discharges used by FAPA and DART are fundamentally different and should have different optimal applications for ambient desorption/ionization mass spectrometry (ADI-MS).

A method of coupling the Paternò-Büchi reaction with direct infusion ESI-MS/MS for locating the C[double bond, length as m-dash]C bond in glycerophospholipids.

PubMed

Stinson, Craig A; Xia, Yu

2016-06-21

Tandem mass spectrometry (MS/MS) coupled with soft ionization is established as an essential platform for lipid analysis; however, determining high order structural information, such as the carbon-carbon double bond (C[double bond, length as m-dash]C) location, remains challenging. Recently, our group demonstrated a method for sensitive and confident lipid C[double bond, length as m-dash]C location determination by coupling online the Paternò-Büchi (PB) reaction with nanoelectrospray ionization (nanoESI) and MS/MS. Herein, we aimed to expand the scope of the PB reaction for lipid analysis by enabling the reaction with infusion ESI-MS/MS at much higher flow rates than demonstrated in the nanoESI setup (∼20 nL min(-1)). In the new design, the PB reaction was effected in a fused silica capillary solution transfer line, which also served as a microflow UV reactor, prior to ESI. This setup allowed PB reaction optimization and kinetics studies. Under optimized conditions, a maximum of 50% PB reaction yield could be achieved for a standard glycerophosphocholine (PC) within 6 s of UV exposure over a wide flow rate range (0.1-10 μL min(-1)). A solvent composition of 7 : 3 acetone : H2O (with 1% acid or base modifier) allowed the highest PB yields and good lipid ionization, while lower yields were obtained with an addition of a variety of organic solvents. Radical induced lipid peroxidation was identified to induce undesirable side reactions, which could be effectively suppressed by eliminating trace oxygen in the solution via N2 purge. Finally, the utility of coupling the PB reaction with infusion ESI-MS/MS was demonstrated by analyzing a yeast polar lipid extract where C[double bond, length as m-dash]C bond locations were revealed for 35 glycerophospholipids (GPs).

Repetitively Pulsed Nonequilibrium Plasmas for Plasma-Assisted Combustion, Flow Control, and Molecular Lasers

NASA Astrophysics Data System (ADS)

Adamovich, Igor

2006-10-01

The paper presents results of three experiments using high voltage, short pulse duration, high repetition rate discharge plasmas. High electric field during the pulse (E/N˜500-1000 Td) allows efficient ionization and molecular dissociation. Between the pulses, additional energy can be coupled to the decaying plasma using a DC field set below the breakdown threshold. While the DC sustainer discharge adds 90-95% of all the power to the flow, it does not produce any additional ionization. The pulser and the sustainer discharges are fully overlapped in space. Low duty cycle of the pulsed ionizer, ˜1/1000, allows sustaining diffuse and uniform pulser-sustainer plasmas at high pressures and power loadings. The first experiment using the pulsed discharge is ignition of premixed hydrocarbon-air flows, which occurs at low pulsed discharge powers, ˜100 W, and very low plasma temperatures, 100-200^0 C. The second experiment is Lorentz force acceleration of low-temperature supersonic flows. The pulsed discharge was used to generate electrical conductivity in M=3 nitrogen and air flows, while the sustainer discharge produced transverse current in the presence of magnetic field of B=1.5 T. Retarding Lorentz force applied to the flow produced a static pressure increase of up to 15-20%, while accelerating force of the same magnitude resulted in static pressure rise of up to 7-8%, i.e. a factor of two smaller. The third experiment is singlet delta oxygen (SDO) generation in a high-pressure pulser-sustainer discharge. SDO yield was inferred from the integrated intensity of SDO infrared emission spectra calibrated using a blackbody source. The measured yield exceeds the laser threshold yield by about a factor of three, which makes possible achieving positive gain in the laser cavity. The highest gain measured so far is 0.03%/cm.

Coupled-cluster treatment of molecular strong-field ionization

NASA Astrophysics Data System (ADS)

Jagau, Thomas-C.

2018-05-01

Ionization rates and Stark shifts of H2, CO, O2, H2O, and CH4 in static electric fields have been computed with coupled-cluster methods in a basis set of atom-centered Gaussian functions with a complex-scaled exponent. Consideration of electron correlation is found to be of great importance even for a qualitatively correct description of the dependence of ionization rates and Stark shifts on the strength and orientation of the external field. The analysis of the second moments of the molecular charge distribution suggests a simple criterion for distinguishing tunnel and barrier suppression ionization in polyatomic molecules.

MPAI (mass probes aided ionization) method for total analysis of biomolecules by mass spectrometry.

PubMed

Honda, Aki; Hayashi, Shinichiro; Hifumi, Hiroki; Honma, Yuya; Tanji, Noriyuki; Iwasawa, Naoko; Suzuki, Yoshio; Suzuki, Koji

2007-01-01

We have designed and synthesized various mass probes, which enable us to effectively ionize various molecules to be detected with mass spectrometry. We call the ionization method using mass probes the "MPAI (mass probes aided ionization)" method. We aim at the sensitive detection of various biological molecules, and also the detection of bio-molecules by a single mass spectrometry serially without changing the mechanical settings. Here, we review mass probes for small molecules with various functional groups and mass probes for proteins. Further, we introduce newly developed mass probes for proteins for highly sensitive detection.

Ionization of EPA Contaminants in Direct and Dopant-Assisted Atmospheric Pressure Photoionization and Atmospheric Pressure Laser Ionization

NASA Astrophysics Data System (ADS)

Kauppila, Tiina J.; Kersten, Hendrik; Benter, Thorsten

2015-06-01

Seventy-seven EPA priority environmental pollutants were analyzed using gas chromatography-mass spectrometry (GC-MS) equipped with an optimized atmospheric pressure photoionization (APPI) and an atmospheric pressure laser ionization (APLI) interface with and without dopants. The analyzed compounds included e.g., polycyclic aromatic hydrocarbons (PAHs), nitro compounds, halogenated compounds, aromatic compounds with phenolic, acidic, alcohol, and amino groups, phthalate and adipatic esters, and aliphatic ethers. Toluene, anisole, chlorobenzene, and acetone were tested as dopants. The widest range of analytes was ionized using direct APPI (66/77 compounds). The introduction of dopants decreased the amount of compounds ionized in APPI (e.g., 54/77 with toluene), but in many cases the ionization efficiency increased. While in direct APPI the formation of molecular ions via photoionization was the main ionization reaction, dopant-assisted (DA) APPI promoted ionization reactions, such as charge exchange and proton transfer. Direct APLI ionized a much smaller amount of compounds than APPI (41/77 compounds), showing selectivity towards compounds with low ionization energies (IEs) and long-lived resonantly excited intermediate states. DA-APLI, however, was able to ionize a higher amount of compounds (e.g. 51/77 with toluene), as the ionization took place entirely through dopant-assisted ion/molecule reactions similar to those in DA-APPI. Best ionization efficiency in APPI and APLI (both direct and DA) was obtained for PAHs and aromatics with O- and N-functionalities, whereas nitro compounds and aliphatic ethers were the most difficult to ionize. Halogenated aromatics and esters were (mainly) ionized in APPI, but not in APLI.

Influence of functional groups on the C α-C β chain of L-phenylalanine and its derivatives

NASA Astrophysics Data System (ADS)

Ganesan, Aravindhan; Brunger, Michael; Wang, Feng

2010-07-01

L-phenylalanine ( L-phe) consists of three different functional groups, i.e., phenyl, carboxyl (-COOH) and amino (-NH 2), joining through the C α-C β bridge. Substitution of these groups produces 2-phenethylamine (PEA) and 3-phenylpropionic acid (PPA). Electronic structures of L-phe, PEA and PPA together with smaller "fragments" L-alanine and benzene were determined using density functional theory (DFT), from which core and valence shell ionization spectra were simulated. Comparison of the spectra reveals that core shell ionization energies clearly indicate that the carbon bridge is significantly affected by their functional group substitutions particularly at the C α site. In the valence space, quite unexpectedly, the frontier orbitals are concentrated on the benzene group although some energy splitting is observed. The orbitals which significantly affect the C α-C β carbon backbone are from the inner valence shell in the ionization energy region of 20-26 eV of the molecules.

A hydrodynamic treatment of the cold dark matter cosmological scenario

NASA Technical Reports Server (NTRS)

Cen, Renyue; Ostriker, Jeremiah

1992-01-01

The evolution of structure in a postrecombination Friedmann-Robertson-Walker universe containing both gaseous baryons and cold dark matter (CDM) is studied by means of an Eulerian code coupled with a standard particle-mesh code. Ionization state and radiative opacity are calculated in detail, and the hydrodynamic simulations make it possible to compute properties of gas distribution on scales larger than three cell sizes. The model yields a soft X-ray background consistent with the latest cosmic nucleosynthesis values, and can accurately reproduce the galaxy-galaxy two-point correlation. The rate of galaxy formation peaks at a relatively late epoch. With regard to mass function, the smallest objects are stabilized against collapse by thermal energy: the mass-weighted mass spectrum peaks in the vicinity of m(b) = 10 exp 9.2 solar masses with a reasonable fit to the Schecter luminosity function if the baryon mass to blue light ratio is approximately 4. Overall, the simulations provide strong support for the CMD scenario. Of particular interest is that, while the baryons are not biased on scales greater than 1/h Mpc, the galaxies are, and that the 'galaxies' have a correlation function of the required slope and the correct amplitude.

Inhibition of quantum transport due to 'scars' of unstable periodic orbits

NASA Technical Reports Server (NTRS)

Jensen, R. V.; Sanders, M. M.; Saraceno, M.; Sundaram, B.

1989-01-01

A new quantum mechanism for the suppression of chaotic ionization of highly excited hydrogen atoms explains the appearance of anomalously stable states in the microwave ionization experiments of Koch et al. A novel phase-space representation of the perturbed wave functions reveals that the inhibition of quantum transport is due to the selective excitation of wave functions that are highly localized near unstable periodic orbits in the chaotic classical phase space. The 'scarred' wave functions provide a new basis for the quantum description of a variety of classically chaotic systems.

Fission-fragment total kinetic energy and mass yields for neutron-induced fission of 235U and 238U with En =200 keV - 30 MeV

NASA Astrophysics Data System (ADS)

Duke, D. L.; Tovesson, F.; Brys, T.; Geppert-Kleinrath, V.; Hambsch, F.-J.; Laptev, A.; Meharchand, R.; Manning, B.; Mayorov, D.; Meierbachtol, K.; Mosby, S.; Perdue, B.; Richman, D.; Shields, D.; Vidali, M.

2017-09-01

The average Total Kinetic Energy (TKE) release and fission-fragment yields in neutron-induced fission of 235U and 238U was measured using a Frisch-gridded ionization chamber. These observables are important nuclear data quantites that are relevant to applications and for informing the next generation of fission models. The measurements were performed a the Los Alamos Neutron Science Center and cover En = 200 keV - 30 MeV. The double-energy (2E) method was used to determine the fission-fragment yields and two methods of correcting for prompt-neutron emission were explored. The results of this study are correlated mass and TKE data.

Atmospheric Fluorescence Yield

NASA Technical Reports Server (NTRS)

Adams, James H., Jr.; Christl, M. J.; Fountain, W. F.; Gregory, J. C.; Martens, K.; Sokolsky, P.; Whitaker, Ann F. (Technical Monitor)

2001-01-01

Several existing and planned experiments estimate the energies of ultra-high energy cosmic rays from air showers using the atmospheric fluorescence from these showers. Accurate knowledge of the conversion from atmospheric fluorescence to energy loss by ionizing particles in the atmosphere is key to this technique. In this paper we discuss a small balloon-borne instrument to make the first in situ measurements versus altitude of the atmospheric fluorescence yield. The instrument can also be used in the lab to investigate the dependence of the fluorescence yield in air on temperature, pressure and the concentrations of other gases that present in the atmosphere. The results can be used to explore environmental effects on and improve the accuracy of cosmic ray energy measurements for existing ground-based experiments and future space-based experiments.

Understanding the flowing atmospheric-pressure afterglow (FAPA) ambient ionization source through optical means.

PubMed

Shelley, Jacob T; Chan, George C-Y; Hieftje, Gary M

2012-02-01

The advent of ambient desorption/ionization mass spectrometry (ADI-MS) has led to the development of a large number of atmospheric-pressure ionization sources. The largest group of such sources is based on electrical discharges; yet, the desorption and ionization processes that they employ remain largely uncharacterized. Here, the atmospheric-pressure glow discharge (APGD) and afterglow of a helium flowing atmospheric-pressure afterglow (FAPA) ionization source were examined by optical emission spectroscopy. Spatial emission profiles of species created in the APGD and afterglow were recorded under a variety of operating conditions, including discharge current, electrode polarity, and plasma-gas flow rate. From these studies, it was found that an appreciable amount of atmospheric H(2)O vapor, N(2), and O(2) diffuses through the hole in the plate electrode into the discharge to become a major source of reagent ions in ADI-MS analyses. Spatially resolved plasma parameters, such as OH rotational temperature (T(rot)) and electron number density (n(e)), were also measured in the APGD. Maximum values for T(rot) and n(e) were found to be ~1100 K and ~4×10(19) m(-3), respectively, and were both located at the pin cathode. In the afterglow, rotational temperatures from OH and N(2)(+) yielded drastically different values, with OH temperatures matching those obtained from infrared thermography measurements. The higher N(2)(+) temperature is believed to be caused by charge-transfer ionization of N(2) by He(2)(+). These findings are discussed in the context of previously reported ADI-MS analyses with the FAPA source. © American Society for Mass Spectrometry, 2011

Understanding the Flowing Atmospheric-Pressure Afterglow (FAPA) Ambient Ionization Source through Optical Means

NASA Astrophysics Data System (ADS)

Shelley, Jacob T.; Chan, George C.-Y.; Hieftje, Gary M.

2012-02-01

The advent of ambient desorption/ionization mass spectrometry (ADI-MS) has led to the development of a large number of atmospheric-pressure ionization sources. The largest group of such sources is based on electrical discharges; yet, the desorption and ionization processes that they employ remain largely uncharacterized. Here, the atmospheric-pressure glow discharge (APGD) and afterglow of a helium flowing atmospheric-pressure afterglow (FAPA) ionization source were examined by optical emission spectroscopy. Spatial emission profiles of species created in the APGD and afterglow were recorded under a variety of operating conditions, including discharge current, electrode polarity, and plasma-gas flow rate. From these studies, it was found that an appreciable amount of atmospheric H2O vapor, N2, and O2 diffuses through the hole in the plate electrode into the discharge to become a major source of reagent ions in ADI-MS analyses. Spatially resolved plasma parameters, such as OH rotational temperature (Trot) and electron number density (ne), were also measured in the APGD. Maximum values for Trot and ne were found to be ~1100 K and ~4 × 1019 m-3, respectively, and were both located at the pin cathode. In the afterglow, rotational temperatures from OH and N{2/+} yielded drastically different values, with OH temperatures matching those obtained from infrared thermography measurements. The higher N{2/+} temperature is believed to be caused by charge-transfer ionization of N2 by He{2/+}. These findings are discussed in the context of previously reported ADI-MS analyses with the FAPA source.

Proteomic Analysis of Trypanosoma cruzi Response to Ionizing Radiation Stress

PubMed Central

Vieira, Helaine Graziele Santos; Grynberg, Priscila; Bitar, Mainá; Pires, Simone da Fonseca; Hilário, Heron Oliveira; Macedo, Andrea Mara; Machado, Carlos Renato; de Andrade, Hélida Monteiro; Franco, Glória Regina

2014-01-01

Trypanosoma cruzi, the causative agent of Chagas disease, is extremely resistant to ionizing radiation, enduring up to 1.5 kGy of gamma rays. Ionizing radiation can damage the DNA molecule both directly, resulting in double-strand breaks, and indirectly, as a consequence of reactive oxygen species production. After a dose of 500 Gy of gamma rays, the parasite genome is fragmented, but the chromosomal bands are restored within 48 hours. Under such conditions, cell growth arrests for up to 120 hours and the parasites resume normal growth after this period. To better understand the parasite response to ionizing radiation, we analyzed the proteome of irradiated (4, 24, and 96 hours after irradiation) and non-irradiated T. cruzi using two-dimensional differential gel electrophoresis followed by mass spectrometry for protein identification. A total of 543 spots were found to be differentially expressed, from which 215 were identified. These identified protein spots represent different isoforms of only 53 proteins. We observed a tendency for overexpression of proteins with molecular weights below predicted, indicating that these may be processed, yielding shorter polypeptides. The presence of shorter protein isoforms after irradiation suggests the occurrence of post-translational modifications and/or processing in response to gamma radiation stress. Our results also indicate that active translation is essential for the recovery of parasites from ionizing radiation damage. This study therefore reveals the peculiar response of T. cruzi to ionizing radiation, raising questions about how this organism can change its protein expression to survive such a harmful stress. PMID:24842666

On the accuracy of density functional theory and wave function methods for calculating vertical ionization energies

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

McKechnie, Scott; Booth, George H.; Cohen, Aron J.

The best practice in computational methods for determining vertical ionization energies (VIEs) is assessed, via reference to experimentally determined VIEs that are corroborated by highly accurate coupled-cluster calculations. These reference values are used to benchmark the performance of density-functional theory (DFT) and wave function methods: Hartree-Fock theory (HF), second-order Møller-Plesset perturbation theory (MP2) and Electron Propagator Theory (EPT). The core test set consists of 147 small molecules. An extended set of six larger molecules, from benzene to hexacene, is also considered to investigate the dependence of the results on molecule size. The closest agreement with experiment is found for ionizationmore » energies obtained from total energy diff calculations. In particular, DFT calculations using exchange-correlation functionals with either a large amount of exact exchange or long-range correction perform best. The results from these functionals are also the least sensitive to an increase in molecule size. In general, ionization energies calculated directly from the orbital energies of the neutral species are less accurate and more sensitive to an increase in molecule size. For the single-calculation approach, the EPT calculations are in closest agreement for both sets of molecules. For the orbital energies from DFT functionals, only those with long-range correction give quantitative agreement with dramatic failing for all other functionals considered. The results offer a practical hierarchy of approximations for the calculation of vertical ionization energies. In addition, the experimental and computational reference values can be used as a standardized set of benchmarks, against which other approximate methods can be compared.« less

Micrometeoroid ablation simulated in the laboratory

NASA Astrophysics Data System (ADS)

Sternovsky, Zoltan; Thomas, Evan W.; DeLuca, Michael; Horanyi, Mihaly; Janches, Diego; Munsat, Tobin L.; Plane, John M. C.

2016-04-01

A facility is developed to simulate the ablation of micrometeoroids in laboratory conditions, which also allows measuring the ionization probability of the ablated material. An electrostatic dust accelerator is used to generate iron and meteoric analog particles with velocities 10-50 km/s. The particles are then introduced into a cell filled with nitrogen, air or carbon dioxide gas with pressures adjustable in the 0.02 - 0.5 Torr range, where the partial or complete ablation of the particle occurs over a short distance. An array of biased electrodes is used to collect the ionized products with spatial resolution along the ablating particles' path, allowing thus the study of the temporal resolution of the process. A simple ablation model is used to match the observations. For completely ablated particles the total collected charge directly yields the ionization efficiency for. The measurements using iron particles in N2 and air are in relatively good agreement with earlier data. The measurements with CO2 and He gases, however, are significantly different from the expectations.

Extreme ultraviolet observations of G191-B2B and the local interstellar medium with the Hopkins Ultraviolet Telescope

NASA Technical Reports Server (NTRS)

Kimble, Randy A.; Davidsen, Arthur F.; Blair, William P.; Bowers, Charles W.; Van Dyke Dixon, W.; Durrance, Samuel T.; Feldman, Paul D.; Ferguson, Henry C.; Henry, Richard C.; Kriss, Gerard A.

1993-01-01

During the Astro-l mission in 1990 December, the Hopkins Ultraviolet Telescope (HUT) was used to observe the extreme ultraviolet spectrum (415-912 A) of the hot DA white dwarf GI91-B2B. Absorption by neutral helium shortward of the 504 A He I absorption edge is clearly detected in the raw spectrum. Model fits to the observed spectrum require interstellar neutral helium and neutral hydrogen column densities of 1.45 +/- 0.065 x 10 exp 17/sq cm and 1.69 +/- 0.12 x 10 exp 18/sq cm, respectively. Comparison of the neutral columns yields a direct assessment of the ionization state of the local interstellar cloud surrounding the Sun. The neutral hydrogen to helium ratio of 11.6 +/- 1.0 observed by HUT strongly contradicts the widespread view that hydrogen is much more ionized than helium in the local interstellar medium, a view which has motivated some exotic theoretical explanations for the supposed high ionization.

Use of propane as a quench gas in argon-filled proportional counters and comparison with other quench gases

NASA Technical Reports Server (NTRS)

Agrawal, P. C.; Ramsey, B. D.

1988-01-01

An experimental investigation of propane and six other quench gases was carried out in argon-filled proportional counters. The objective of the study was to find the best gas mixture for optimizing the gas gain and the energy resolution as well as to understand the role of the ionization potential of quench gases in determining these parameters. It was found that the best gas gains and energy resolutions are obtained with propane, ethane, and isobutane in that order. The ionization potentials of these three lie below the argon metastable potentials and have the lowest value of resonance defect compared to the other quench gases. The better results obtained with these mixtures can be explained by an increased ionization yield resulting from the Penning effect. Propylene and trans-2-butene give inferior performance compared to the above three gases. Methane and carbon dioxide, the most commonly used quench gases in the argon-filled detectors, provide the worst results.

The importance of Rydberg orbitals in dissociative ionization of small hydrocarbon molecules in intense laser fields.

PubMed

Jochim, Bethany; Siemering, R; Zohrabi, M; Voznyuk, O; Mahowald, J B; Schmitz, D G; Betsch, K J; Berry, Ben; Severt, T; Kling, Nora G; Burwitz, T G; Carnes, K D; Kling, M F; Ben-Itzhak, I; Wells, E; de Vivie-Riedle, R

2017-06-30

Much of our intuition about strong-field processes is built upon studies of diatomic molecules, which typically have electronic states that are relatively well separated in energy. In polyatomic molecules, however, the electronic states are closer together, leading to more complex interactions. A combined experimental and theoretical investigation of strong-field ionization followed by hydrogen elimination in the hydrocarbon series C 2 D 2 , C 2 D 4 and C 2 D 6 reveals that the photofragment angular distributions can only be understood when the field-dressed orbitals rather than the field-free orbitals are considered. Our measured angular distributions and intensity dependence show that these field-dressed orbitals can have strong Rydberg character for certain orientations of the molecule relative to the laser polarization and that they may contribute significantly to the hydrogen elimination dissociative ionization yield. These findings suggest that Rydberg contributions to field-dressed orbitals should be routinely considered when studying polyatomic molecules in intense laser fields.

The effects of pre-ionization using a shunt resistor on reproducibility of the x-ray emission in a dense plasma focus device

NASA Astrophysics Data System (ADS)

Piriaei, D.; Yousefi, H. R.; Mahabadi, T. D.; SalarElahi, A.; Ghoranneviss, M.

2017-08-01

In this research, the effects of pre-ionization using a shunt resistor on reproducibility of x-ray emission in a Mather type plasma focus device have been studied. This technique increased the intensities of the emitted x-rays from argon as the filling gas of the device and made the x-ray yields with similar intensities reproducible. A Mirnov coil was also used to record the variations of the plasma's magnetic field, and the wavelet spectrums of these recorded signals showed the reduced instabilities due to the application of the pre-ionization technique. Moreover, it was demonstrated that this technique was capable of reducing the number of initial runaway electrons that could increase the impurities and instabilities inside the plasma. In addition to the above-mentioned features, this technique could improve the uniform formation of the current sheath during the breakdown phase that might later lead to a high quality pinch and high intensity emitted x-rays.

Atmospheric Pressure Ionization Using a High Voltage Target Compared to Electrospray Ionization.

PubMed

Lubin, Arnaud; Bajic, Steve; Cabooter, Deirdre; Augustijns, Patrick; Cuyckens, Filip

2017-02-01

A new atmospheric pressure ionization (API) source, viz. UniSpray, was evaluated for mass spectrometry (MS) analysis of pharmaceutical compounds by head-to-head comparison with electrospray ionization (ESI) on the same high-resolution MS system. The atmospheric pressure ionization source is composed of a grounded nebulizer spraying onto a high voltage, cylindrical stainless steel target. Molecules are ionized in a similar fashion to electrospray ionization, predominantly producing protonated or deprotonated species. Adduct formation (e.g., proton and sodium adducts) and in-source fragmentation is shown to be almost identical between the two sources. The performance of the new API source was compared with electrospray by infusion of a mix of 22 pharmaceutical compounds with a wide variety of functional groups and physico-chemical properties (molecular weight, logP, and pKa) in more than 100 different conditions (mobile phase strength, solvents, pH, and flow rate). The new API source shows an intensity gain of a factor 2.2 compared with ESI considering all conditions on all compounds tested. Finally, some hypotheses on the ionization mechanism, similarities, and differences with ESI, are discussed. Graphical Abstract ᅟ.

Atmospheric Pressure Ionization Using a High Voltage Target Compared to Electrospray Ionization

NASA Astrophysics Data System (ADS)

Lubin, Arnaud; Bajic, Steve; Cabooter, Deirdre; Augustijns, Patrick; Cuyckens, Filip

2017-02-01

A new atmospheric pressure ionization (API) source, viz. UniSpray, was evaluated for mass spectrometry (MS) analysis of pharmaceutical compounds by head-to-head comparison with electrospray ionization (ESI) on the same high-resolution MS system. The atmospheric pressure ionization source is composed of a grounded nebulizer spraying onto a high voltage, cylindrical stainless steel target. Molecules are ionized in a similar fashion to electrospray ionization, predominantly producing protonated or deprotonated species. Adduct formation (e.g., proton and sodium adducts) and in-source fragmentation is shown to be almost identical between the two sources. The performance of the new API source was compared with electrospray by infusion of a mix of 22 pharmaceutical compounds with a wide variety of functional groups and physico-chemical properties (molecular weight, logP, and pKa) in more than 100 different conditions (mobile phase strength, solvents, pH, and flow rate). The new API source shows an intensity gain of a factor 2.2 compared with ESI considering all conditions on all compounds tested. Finally, some hypotheses on the ionization mechanism, similarities, and differences with ESI, are discussed.

[Ionization energies and infrared spectra studies of histidine using density functional theory].

PubMed

Hu, Qiong; Wang, Guo-Ying; Liu, Gang; Ou, Jia-Ming; Wang, Rui-Li

2010-05-01

Histidines provide axial ligands to the primary electron donors in photosynthetic reaction centers (RCs) and play an important role in the protein environments of these donors. In this paper the authors present a systematic study of ionization energies and vibrational properties of histidine using hybrid density functional theory (DFT). All calculations were undertaken by using B3LYP method in combination with four basis sets: 6-31G(d), 6-31G(df, p), 6-31+G(d) and 6-311+G(2d, 2p) with the aim to investigate how the basis sets influence the calculation results. To investigate solvent effects and gain a detailed understanding of marker bands of histidine, the ionization energies of histidine and the vibrational frequencies of histidine which are unlabeled and 13C, 15N, and 2H labeled in the gas phase, CCl4, protein environment, THF and water solution, which span a wide range of dielectric constant, were also calculated. Our results showed that: (1) The main geometry parameters of histidine were impacted by basis sets and mediums, and C2-N3 and N3-C4 bond of imidazole ring of histidine side chain display the maximum bond lengths in the gas phase; (2) single point energies and frequencies calculated were decreased while ionization energies increased with the increasing level of basis sets and diffuse function applied in the same solvent; (3) with the same computational method, the higher the dielectric constant of the solvent used, the lower the ionization energy and vibrational frequency and the higher the intensity obtained. In addition, calculated ionization energy in the gas phase and marker bands of histidine as well as frequency shift upon 13C and 15N labeling at the computationally more expensive 6-311+G(2d, 2p) level are in good agreement with experimental observations available in literatures. All calculations indicated that the results calculated by using higher level basis set with diffuse function were more accurate and closer to the experimental value. In conclusion, the results provide useful information for the further studies of the functional and vibrational properties of chlorophyll-a ligated to histidine residue in photosynthetic reaction center.

FAMBE-pH: A Fast and Accurate Method to Compute the Total Solvation Free Energies of Proteins

PubMed Central

Vorobjev, Yury N.; Vila, Jorge A.

2009-01-01

A fast and accurate method to compute the total solvation free energies of proteins as a function of pH is presented. The method makes use of a combination of approaches, some of which have already appeared in the literature; (i) the Poisson equation is solved with an optimized fast adaptive multigrid boundary element (FAMBE) method; (ii) the electrostatic free energies of the ionizable sites are calculated for their neutral and charged states by using a detailed model of atomic charges; (iii) a set of optimal atomic radii is used to define a precise dielectric surface interface; (iv) a multilevel adaptive tessellation of this dielectric surface interface is achieved by using multisized boundary elements; and (v) 1:1 salt effects are included. The equilibrium proton binding/release is calculated with the Tanford–Schellman integral if the proteins contain more than ∼20–25 ionizable groups; for a smaller number of ionizable groups, the ionization partition function is calculated directly. The FAMBE method is tested as a function of pH (FAMBE-pH) with three proteins, namely, bovine pancreatic trypsin inhibitor (BPTI), hen egg white lysozyme (HEWL), and bovine pancreatic ribonuclease A (RNaseA). The results are (a) the FAMBE-pH method reproduces the observed pKa's of the ionizable groups of these proteins within an average absolute value of 0.4 pK units and a maximum error of 1.2 pK units and (b) comparison of the calculated total pH-dependent solvation free energy for BPTI, between the exact calculation of the ionization partition function and the Tanford–Schellman integral method, shows agreement within 1.2 kcal/mol. These results indicate that calculation of total solvation free energies with the FAMBE-pH method can provide an accurate prediction of protein conformational stability at a given fixed pH and, if coupled with molecular mechanics or molecular dynamics methods, can also be used for more realistic studies of protein folding, unfolding, and dynamics, as a function of pH. PMID:18683966

A Versatile Integrated Ambient Ionization Source Platform.

PubMed

Ai, Wanpeng; Nie, Honggang; Song, Shiyao; Liu, Xiaoyun; Bai, Yu; Liu, Huwei

2018-04-30

The pursuit of high-throughput sample analysis from complex matrix demands development of multiple ionization techniques with complementary specialties. A versatile integrated ambient ionization source (iAmIS) platform is proposed in this work, based on the idea of integrating multiple functions, enhancing the efficiency of current ionization techniques, extending the applications, and decreasing the cost of the instrument. The design of the iAmIS platform combines flowing atmospheric pressure afterglow (FAPA) source/direct analysis in real time (DART), dielectric barrier discharge ionization (DBDI)/low-temperature plasma (LTP), desorption electrospray ionization (DESI), and laser desorption (LD) technique. All individual and combined ionization modes can be easily attained by modulating parameters. In particular, the FAPA/DART&DESI mode can realize the detection of polar and nonpolar compounds at the same time with two different ionization mechanisms: proton transfer and charge transfer. The introduction of LD contributes to the mass spectrometry imaging and the surface-assisted laser desorption (SALDI) under ambient condition. Compared with other individual or multi-mode ion source, the iAmIS platform provides the flexibility of choosing different ionization modes, broadens the scope of the analyte detection, and facilitates the analysis of complex samples. Graphical abstract ᅟ.

Spontaneous-Desorption Ionizer for a TOF-MS

NASA Technical Reports Server (NTRS)

Schultz, J. Albert

2006-01-01

A time-of-flight mass spectrometer (TOF-MS) like the one mentioned in the immediately preceding article has been retrofitted with an ionizer based on a surface spontaneous-desorption process. This ionizer includes an electron multiplier in the form of a microchannel plate (MCP). Relative to an ionizer based on a hot-filament electron source, this ionizer offers advantages of less power consumption and greater mechanical ruggedness. The current density and stability characteristics of the electron emission of this ionizer are similar to those of a filament-based ionizer. In tests of various versions of this ionizer in the TOF-MS, electron currents up to 100 nA were registered. Currents of microamperes or more - great enough to satisfy requirements in most TOFMS applications - could be obtained by use of MCPs different from those used in the tests, albeit at the cost of greater bulk. One drawback of this ionizer is that the gain of the MCP decreases as a function of the charge extracted thus far; the total charge that can be extracted over the operational lifetime is about 1 coulomb. An MCP in the ion-detector portion of the TOF-MS is subject to the same limitation.

A Versatile Integrated Ambient Ionization Source Platform

NASA Astrophysics Data System (ADS)

Ai, Wanpeng; Nie, Honggang; Song, Shiyao; Liu, Xiaoyun; Bai, Yu; Liu, Huwei

2018-04-01

The pursuit of high-throughput sample analysis from complex matrix demands development of multiple ionization techniques with complementary specialties. A versatile integrated ambient ionization source (iAmIS) platform is proposed in this work, based on the idea of integrating multiple functions, enhancing the efficiency of current ionization techniques, extending the applications, and decreasing the cost of the instrument. The design of the iAmIS platform combines flowing atmospheric pressure afterglow (FAPA) source/direct analysis in real time (DART), dielectric barrier discharge ionization (DBDI)/low-temperature plasma (LTP), desorption electrospray ionization (DESI), and laser desorption (LD) technique. All individual and combined ionization modes can be easily attained by modulating parameters. In particular, the FAPA/DART&DESI mode can realize the detection of polar and nonpolar compounds at the same time with two different ionization mechanisms: proton transfer and charge transfer. The introduction of LD contributes to the mass spectrometry imaging and the surface-assisted laser desorption (SALDI) under ambient condition. Compared with other individual or multi-mode ion source, the iAmIS platform provides the flexibility of choosing different ionization modes, broadens the scope of the analyte detection, and facilitates the analysis of complex samples. [Figure not available: see fulltext.

Conformational analyses of 2,3-dihydroxypropanoic acid as a function of solvent and ionization state as determined by NMR spectroscopy.

PubMed

Drake, Michael D; Harsha, Alex K; Terterov, Sergei; Roberts, John D

2006-03-01

Vicinal (1)H--(1)H coupling constants were used to determine the conformational preferences of 2,3-dihydroxypropanoic acid (1) (DL-glyceric acid) in various solvents and its different carboxyl ionization states. The stereospecific assignments of J(12) and J(13) were confirmed through the point-group substitution of the C-3 hydrogen with deuterium, yielding rac-(2SR,3RS)-[3-(2)H]-1, and the observation of only J(13) in the (1)H NMR spectra. While hydrogen bonding and steric strain may be expected to drive the conformational equilibrium, their role is overshadowed by a profound gauche effect between the vicinal hydroxyl groups that mimics other substituted ethanes, such as 1,2-ethanediol and 1,2-difluoroethane. At low pH, the conformational equilibrium is heavily weighted toward the gauche-hydroxyl rotamers with a range of 81% in DMSO-d(6) to 92% in tert-butyl alcohol-d(10). At high pH, the equilibrium exhibits a larger dependence upon the polarity and solvating capability of the medium, although the gauche effect still dominates in D(2)O, 1,4-dioxane-d(8), methanol-d(4), and ethanol-d(6) (96, 89, 85, and 83% gauche-hydroxyls respectively). The observed preference for the gauche-hydroxyl rotamers is believed to stem primarily from hyperconjugative sigma(C--H) --> sigma*(C--OH) interactions.

Dissociation dynamics of 3- and 4-nitrotoluene radical cations: Coherently driven C-NO2 bond homolysis

NASA Astrophysics Data System (ADS)

Ampadu Boateng, Derrick; Gutsev, Gennady L.; Jena, Puru; Tibbetts, Katharine Moore

2018-04-01

Monosubstituted nitrotoluenes serve as important model compounds for nitroaromatic energetic molecules such as trinitrotoluene. This work investigates the ultrafast nuclear dynamics of 3- and 4-nitrotoluene radical cations using femtosecond pump-probe measurements and the results of density functional theory calculations. Strong-field adiabatic ionization of 3- and 4-nitrotoluene using 1500 nm, 18 fs pulses produces radical cations in the ground electronic state with distinct coherent vibrational excitations. In both nitrotoluene isomers, a one-photon excitation with the probe pulse results in NO2 loss to form C7H7+, which exhibits out-of-phase oscillations in yield with the parent molecular ion. The oscillations in 4-nitrotoluene with a period of 470 fs are attributed to the torsional motion of the NO2 group based on theoretical results showing that the dominant relaxation pathway in 4-nitrotoluene radical cations involves the rotation of the NO2 group away from the planar geometry. The distinctly faster oscillation period of 216 fs in 3-nitrotoluene is attributed to an in-plane bending motion of the NO2 and CH3 moieties based on analysis of the normal modes. These results demonstrate that coherent nuclear motions determine the probability of C-NO2 homolysis in the nitrotoluene radical cations upon optical excitation within several hundred femtoseconds of the initial ionization event.

Hybrid-PIC Modeling of the Transport of Atomic Boron in a Hall Thruster

NASA Technical Reports Server (NTRS)

Smith, Brandon D.; Boyd, Iaian D.; Kamhawi, Hani

2015-01-01

Computational analysis of the transport of boron eroded from the walls of a Hall thruster is performed by implementing sputter yields of hexagonal boron nitride and velocity distribution functions of boron within the hybrid-PIC model HPHall. The model is applied to simulate NASA's HiVHAc Hall thruster at a discharge voltage of 500V and discharge powers of 1-3 kW. The number densities of ground- and 4P-state boron are computed. The density of ground-state boron is shown to be a factor of about 30 less than the plasma density. The density of the excited state is shown to be about three orders of magnitude less than that of the ground state, indicating that electron impact excitation does not significantly affect the density of ground-state boron in the discharge channel or near-field plume of a Hall thruster. Comparing the rates of excitation and ionization suggests that ionization has a greater influence on the density of ground-state boron, but is still negligible. The ground-state boron density is then integrated and compared to cavity ring-down spectroscopy (CRDS) measurements for each operating point. The simulation results show good agreement with the measurements for all operating points and provide evidence in support of CRDS as a tool for measuring Hall thruster erosion in situ.

Fission fragment yields and total kinetic energy release in neutron-induced fission of235,238U,and239Pu

NASA Astrophysics Data System (ADS)

Tovesson, F.; Duke, D.; Geppert-Kleinrath, V.; Manning, B.; Mayorov, D.; Mosby, S.; Schmitt, K.

2018-03-01

Different aspects of the nuclear fission process have been studied at Los Alamos Neutron Science Center (LANSCE) using various instruments and experimental techniques. Properties of the fragments emitted in fission have been investigated using Frisch-grid ionization chambers, a Time Projection Chamber (TPC), and the SPIDER instrument which employs the 2v-2E method. These instruments and experimental techniques have been used to determine fission product mass yields, the energy dependent total kinetic energy (TKE) release, and anisotropy in neutron-induced fission of U-235, U-238 and Pu-239.

Reionization of Hydrogen and Helium by Early Stars and Quasars

NASA Astrophysics Data System (ADS)

Wyithe, J. Stuart B.; Loeb, Abraham

2003-04-01

We compute the reionization histories of hydrogen and helium caused by the ionizing radiation fields produced by stars and quasars. For the quasars we use a model based on halo-merger rates that reproduces all known properties of the quasar luminosity function at high redshifts. The less constrained properties of the ionizing radiation produced by stars are modeled with two free parameters: (i) a transition redshift, ztran, above which the stellar population is dominated by massive, zero-metallicity stars and below which it is dominated by a Scalo mass function; and (ii) the product of the escape fraction of stellar ionizing photons from their host galaxies and the star formation efficiency, fescf*. We constrain the allowed range of these free parameters at high redshifts on the basis of the lack of the H I Gunn-Peterson trough at z<~6 and the upper limit on the total intergalactic optical depth for electron scattering, τes<0.18, from recent cosmic microwave background (CMB) experiments. We find that quasars ionize helium by a redshift z~4, but cannot reionize hydrogen by themselves before z~6. A major fraction of the allowed combinations of fescf* and ztran leads to an early peak in the ionized fraction because of the presence of metal-free stars at high redshifts. This sometimes results in two reionization epochs, namely, an early H II or He III overlap phase followed by recombination and a second overlap phase. Even if early overlap is not achieved, the peak in the visibility function for scattering of the CMB often coincides with the early ionization phase rather than with the actual reionization epoch. Consequently, τes does not correspond directly to the reionization redshift. We generically find values of τes>~7%, which should be detectable by the MAP satellite.

Dielectric barrier discharge ionization for liquid chromatography/mass spectrometry.

PubMed

Hayen, Heiko; Michels, Antje; Franzke, Joachim

2009-12-15

An atmospheric pressure microplasma ionization source based on a dielectric barrier discharge with a helium plasma cone outside the electrode region has been developed for liquid chromatography/mass spectrometry (LC/MS). For this purpose, the plasma was realized in a commercial atmospheric pressure ionization source. Dielectric barrier discharge ionization (DBDI) was compared to conventional electrospray ionization (ESI), atmospheric pressure chemical ionization (APCI), and atmospheric pressure photoionization (APPI) in the positive ionization mode. Therefore, a heterogeneous compound library was investigated that covered polar compounds such as amino acids, water-soluble vitamins, and nonpolar compounds like polycyclic aromatic hydrocarbons and functionalized hydrocarbons. It turned out that DBDI can be regarded as a soft ionization technique characterized by only minor fragmentation similar to APCI. Mainly protonated molecules were detected. Additionally, molecular ions were observed for polycyclic aromatic hydrocarbons and derivatives thereof. During DBDI, adduct formation with acetonitrile occurred. For aromatic compounds, addition of one to four oxygen atoms and to a smaller extend one nitrogen and oxygen was observed which delivered insight into the complexity of the ionization processes. In general, compounds covering a wider range of polarities can be ionized by DBDI than by ESI. Furthermore, limits of detection compared to APCI are in most cases equal or even better.

Electron Resonance Decay into a Biological Function: Decrease in Viability of E. coli Transformed by Plasmid DNA Irradiated with 0.5-18 eV Electrons.

PubMed

Kouass Sahbani, S; Cloutier, P; Bass, A D; Hunting, D J; Sanche, L

2015-10-01

Transient negative ions (TNIs) are ubiquitous in electron-molecule scattering at low electron impact energies (0-20 eV) and are particularly effective in damaging large biomolecules. Because ionizing radiation generates mostly 0-20 eV electrons, TNIs are expected to play important roles in cell mutagenesis and death during radiotherapeutic cancer treatment, although this hypothesis has never been directly verified. Here, we measure the efficiency of transforming E. coli bacteria by inserting into the cells, pGEM-3ZfL(-) plasmid DNA that confers resistance to the antibiotic ampicillin. Before transformation, plasmids are irradiated with electrons of specific energies between 0.5 and 18 eV. The loss of transformation efficiency plotted as a function of irradiation energy reveals TNIs at 5.5 and 9.5 eV, corresponding to similar states observed in the yields of DNA double strand breaks. We show that TNIs are detectable in the electron-energy dependence of a biological process and can decrease cell viability.

Spectroscopic studies and quantum chemical investigations of (3,4-dimethoxybenzylidene) propanedinitrile

NASA Astrophysics Data System (ADS)

Gupta, Ujval; Kumar, Vinay; Singh, Vivek K.; Kant, Rajni; Khajuria, Yugal

2015-04-01

The Fourier Transform Infrared (FTIR), Ultra-Violet Visible (UV-Vis) spectroscopy and Thermogravimetric (TG) analysis of (3,4-dimethoxybenzylidene) propanedinitrile have been carried out and investigated using quantum chemical calculations. The molecular geometry, harmonic vibrational frequencies, Mulliken charges, natural atomic charges and thermodynamic properties in the ground state have been investigated by using Hartree Fock Theory (HF) and Density Functional Theory (DFT) using B3LYP functional with 6-311G(d,p) basis set. Both HF and DFT methods yield good agreement with the experimental data. Vibrational modes are assigned with the help of Vibrational Energy Distribution Analysis (VEDA) program. UV-Visible spectrum was recorded in the spectral range of 190-800 nm and the results are compared with the calculated values using TD-DFT approach. Stability of the molecule arising from hyperconjugative interactions, charge delocalization have been analyzed using natural bond orbital (NBO) analysis. The results obtained from the studies of Highest Occupied Molecular Orbital (HOMO) and Lowest Unoccupied Molecular Orbital (LUMO) are used to calculate molecular parameters like ionization potential, electron affinity, global hardness, electron chemical potential and global electrophilicity.

Oxygen adsorption on a Si(1 0 0) substrate: effects on secondary emission properties

NASA Astrophysics Data System (ADS)

Vogan, W. S.; Champion, R. L.

2001-10-01

Secondary anion and electron yields resulting from low-energy (50-500 eV) Na + bombardment of an oxygen-adsorbed Si(1 0 0) substrate have been measured as a function of oxygen exposure and of Na + impact energy. Adsorbate coverage ranges from none to over half a monolayer. The dominant sputtered anion was found to be O - with SiO 2- being a minor constituent. Kinetic energy distributions of the secondary anions and electrons were also measured. The presence of an adsorbate was observed to enhance secondary anion emission to a significant degree whereas secondary electron emission was minor, in sharp contrast to what has been observed for metallic substrates. The mechanism for secondary emission appears to involve electronic excitation of Si xO -; it is suggested that electron emission is governed by a process similar to Penning ionization, in which a vacancy created by the excitation of Si xO - may be filled by an electron from the valence band. The variation in the work function as oxygen accumulated on the surface was observed to be small.

Furfural: The Unimolecular Dissociative Photoionization Mechanism of the Simplest Furanic Aldehyde.

PubMed

Winfough, Matthew; Voronova, Krisztina; Muller, Giel; Laguisma, Gabrielle; Sztáray, Bálint; Bodi, Andras; Meloni, Giovanni

2017-05-11

The unimolecular dissociation reactions of energy-selected furfural cations have been studied by imaging photoelectron photoion coincidence spectroscopy at the vacuum-ultraviolet (VUV) beamline of the Swiss Light Source. In the photon energy range of 10.9-14.5 eV, furfural ions decay by numerous fragmentation channels. Modeling the breakdown diagram yielded the 0 K appearance energies of 10.95 ± 0.10, 11.16, and 12.03 eV for the c-C 4 H 3 O-CO + (m/z = 95), c-C 4 H 4 O + (m/z = 68), and c-C 3 H 3 + (m/z = 39) fragment ions, respectively, formed by parallel dissociation channels. An internal conversion from the A″ to the A' electronic state via a conical intersection takes place along the reaction coordinate in the case of the H-loss channel (c-C 4 H 3 O-CO + formation). Quantum chemical calculations and experimental results confirmed a fast conversion to the A' state and that the rate-determining step is a tight transition state on the potential energy surface. Appearance energies were also derived for the sequential dissociation products from the furan cation, c-C 4 H 4 O + , for the formation of CH 2 CO + (m/z = 42), C 3 H 4 + (m/z = 40), and CHO + (m/z = 29) at 12.81, 12.80, and 13.34 eV, respectively. Statistical rate theory modeling of the breakdown diagram can also be used to predict the fractional ion abundances and thermal shifts in mass spectrometric pyrolysis studies to help assigning the m/z channels either to ionization of the neutrals or to dissociative ionization processes, with potential use for combustion diagnostics. The cationic geometry optimizations yielded functional-dependent spurious DFT minima and a deviating planar MP2 optimized geometry, which are briefly discussed.

On-surface Fenton and Fenton-like reactions appraised by paper spray ionization mass spectrometry.

PubMed

Resende, S F; Oliveira, B S; Augusti, R

2018-06-21

On-surface degradation of sildenafil (an adequate substrate as it contains assorted functional groups in its structure) promoted by the Fenton (Fe 2+ / H 2 O 2 ) and Fenton-like (M n+ / H 2 O 2 ; M n+ = Fe 3+ , Co 2+ , Cu 2+ , Mn 2+ ) systems was investigated by using paper spray ionization mass spectrometry (PS-MS). The performance of each system was compared by measuring the ratio between the relative intensities of the ions of m/z 475 (protonated sildenafil) and m/z 235 (protonated lidocaine, used as a convenient internal standard and added to the paper just before the PS-MS analyzes). The results indicated the following order in the rates of such reactions: Fe 2+ /H 2 O 2 > H 2 O 2 > Cu 2+ /H 2 O 2 > M n+ / H 2 O 2 (M n+ = Fe 3+ , Co 2+ , Mn 2+ ) ~ M n+ (M n+ = Fe 2+ , Fe 3+ , Co 2+ , Cu 2+ , Mn 2 . The superior capability of Fe 2+ /H 2 O 2 in causing the degradation of sildenafil indicates that Fe 2+ efficiently decomposes H 2 O 2 to yield hydroxyl radicals, quite reactive species that cause the substrate oxidation. The results also indicate that H 2 O 2 can spontaneously decompose likely to yield hydroxyl radicals, although in a much smaller extension than the Fenton system. This effect, however, is strongly inhibited by the presence of the other cations, i. e. Fe 3+ , Co 2+ , Cu 2+ and Mn 2+ . A unique oxidation by-product was detected in the reaction between Fe 2+ /H 2 O 2 with sildenafil and a possible structure for it was proposed based on the MS/MS data. The on-surface reaction of other substrates (trimethoprim and tamoxifen) with the Fenton system was also investigated. In conclusion, PS-MS shown to be a convenient platform to promptly monitor on-surface oxidation reactions. This article is protected by copyright. All rights reserved.

Double photoionization of propylene oxide: A coincidence study of the ejection of a pair of valence-shell electrons

NASA Astrophysics Data System (ADS)

Falcinelli, Stefano; Vecchiocattivi, Franco; Alagia, Michele; Schio, Luca; Richter, Robert; Stranges, Stefano; Catone, Daniele; Arruda, Manuela S.; Mendes, Luiz A. V.; Palazzetti, Federico; Aquilanti, Vincenzo; Pirani, Fernando

2018-03-01

Propylene oxide, a favorite target of experimental and theoretical studies of circular dichroism, was recently discovered in interstellar space, further amplifying the attention to its role in the current debate on protobiological homochirality. In the present work, a photoelectron-photoion-photoion coincidence technique, using an ion-imaging detector and tunable synchrotron radiation in the 18.0-37.0 eV energy range, permits us (i) to observe six double ionization fragmentation channels, their relative yields being accounted for about two-thirds by the couple (C2H4+, CH2O+) and one-fifth by (C2H3+, CH3O+); (ii) to measure thresholds for their openings as a function of photon energy; and (iii) to unravel a pronounced bimodality for a kinetic-energy-released distribution, fingerprint of competitive non-adiabatic mechanisms.

Concerning the Role of Supercritical Carbon Dioxide in SN 1 Reactions.

PubMed

Qiao, Yun X; Theyssen, Nils; Eifert, Tobias; Liauw, Marcel A; Franciò, Giancarlo; Schenk, Karolin; Leitner, Walter; Reetz, Manfred T

2017-03-17

A series of S N 1-type reactions has been studied under various conditions to clarify the role of supercritical carbon dioxide (scCO 2 ) as reaction medium for this kind of transformations. The application of scCO 2 did not result in higher yields in any of the experiments in comparison to those under neat conditions or in the presence of other inert compressed gases. High-pressure UV/Vis spectroscopic measurements were carried out to quantify the degree of carbocation formation of a highly S N 1-active alkyl halide as a function of the applied solvent. No measureable concentration of carbocations could be detected in scCO 2 , just like in other low polarity solvents. Taken together, these results do not support the previously claimed activating effect via enhanced S N 1 ionization due to the quadrupolar moment of the supercritical fluid. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis and characterization of stimuli-responsive polypropylene containing N-vinylcaprolactam and N-vinylimidazole obtained by ionizing radiation.

PubMed

Zavala-Lagunes, Edgar; Ruiz, Juan-Carlos; Varca, Gustavo H C; Bucio, Emilio

2016-10-01

Polypropylene films were grafted with thermo-responsive N-vinylcaprolactam and pH-responsive N-vinylimidazole polymers by means of gamma radiation using pre-irradiation and direct methods, in order to functionalize the films with thermo- and/or pH-responsiveness. The dependence of grafting yield on parameters such as co-monomer concentration, pre-irradiation dose, temperature, and reaction time was evaluated. The samples were characterized by Fourier transform infrared and X-ray photoelectron spectroscopies, differential scanning calorimetry, thermogravimetric analysis, swelling studies in different solvents, and water contact angle. The grafted copolymers presented thermo- and pH-sensitiveness, highlighting their potential as advanced biomaterials, capable of providing adequate environment for hosting and sustained release of antimicrobial drugs bearing cationic moieties, such as groups of diclofenac, while still exhibiting good cytocompatibility. Copyright © 2016 Elsevier B.V. All rights reserved.

GaAs MMIC: recovery from upset by x-ray pulse

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

Armendariz, M.G.; Castle, J.G. Jr.

1986-01-01

Tolerance for fast neutrons and total ionizing dose is a feature of GaAs microwave monolithic integrated circuits (MMIC). However, upset during an ionizing pulse is expected to occur and delayed recovery due to backgating may be a problem. The purpose of this study of an experimental MMIC design is to observe the recovery of oscillator power output following upset by a short ionizing pulse as a function of applied bias, dose per pulse and case temperature.

Web application for studying the free energy of binding and protonation states of protein-ligand complexes based on HINT

PubMed Central

Bayden, Alexander S.; Fornabaio, Micaela; Scarsdale, J. Neel

2009-01-01

A public web server performing computational titration at the active site in a protein-ligand complex has been implemented. This calculation is based on the Hydropathic INTeraction (HINT) noncovalent force field. From 3D coordinate data for the protein, ligand and bridging waters (if available), the server predicts the best combination of protonation states for each ionizable residue and/or ligand functional group as well as the Gibbs free energy of binding for the ionization-optimized protein-ligand complex. The 3D structure for the modified molecules is available as output. In addition, a graph depicting how this energy changes with acidity, i.e., as a function of added protons, can be obtained. This data may prove to be of use in preparing models for virtual screening and molecular docking. A few illustrative examples are presented. In β secretase (2va7) computational titration flipped the amide groups of Gln12 and Asn37 and protonated a ligand amine yielding an improvement of 6.37 kcal mol−1 in the protein-ligand binding score. Protonation of Glu139 in mutant HIV-1 reverse transcriptase (2opq) allows a water bridge between the protein and inhibitor that increases the protein-ligand interaction score by 0.16 kcal mol−1. In human sialidase NEU2 complexed with an isobutyl ether mimetic inhibitor (2f11) computational titration suggested that protonating Glu218, deprotonating Arg237, flipping the amide bond on Tyr334, and optimizing the positions of several other polar protons would increase the protein-ligand interaction score by 0.71 kcal mol−1. PMID:19554265

Chemistry of α-pinene and naphthalene oxidation products generated in a Potential Aerosol Mass (PAM) chamber as measured by acetate chemical ionization mass spectrometry

DOE PAGES

Chhabra, P. S.; Lambe, A. T.; Canagaratna, M. R.; ...

2014-07-01

Recent developments in high resolution, time-of-flight chemical ionization mass spectrometry (HR-ToF-CIMS) have made possible the direct detection of atmospheric organic compounds in real-time with high sensitivity and with little or no fragmentation, including low volatility, highly oxygenated organic vapors that are precursors to secondary organic aerosol formation. Here, for the first time, we examine gas-phase O 3 and OH oxidation products of α-pinene and naphthalene formed in the PAM flow reactor with an HR-ToF-CIMS using acetate reagent ion chemistry. Integrated OH exposures ranged from 1.2 × 10 11 to 9.7 × 10 11 molec cm −3 s, corresponding to approximatelymore » 1.0 to 7.5 days of equivalent atmospheric oxidation. Measured gas-phase organic acids are similar to those previously observed in environmental chamber studies. For both precursors, we find that acetate-CIMS spectra capture both functionalization (oxygen addition) and fragmentation (carbon loss) as a function of OH exposure. The level of fragmentation is observed to increase with increased oxidation. We present a method that estimates vapor pressures of organic molecules using the measured O/C ratio, H/C ratio, and carbon number for each compound detected by the CIMS. The predicted condensed-phase SOA average acid yields and O/C and H/C ratios agree within uncertainties with previous AMS measurements and ambient CIMS results. While acetate reagent ion chemistry is used to selectively measure organic acids, in principle this method can be applied to additional reagent ion chemistries depending on the application.« less

Conduction in fully ionized liquid metals

NASA Technical Reports Server (NTRS)

Stevenson, D. J.; Ashcroft, N. W.

1973-01-01

Electron transport is considered in high density fully ionized liquid metals. Ionic structure is described in terms of hard-sphere correlation functions and the scattering is determined from self-consistently screened point ions. Applications to the physical properties of the deep interior of Jupiter are briefly considered.

Zero kinetic energy spectroscopy: mass-analyzed threshold ionization spectra of chromium sandwich complexes with alkylbenzenes, (η(6)-RPh)(2)Cr (R = Me, Et, i-Pr, t-Bu).

PubMed

Ketkov, Sergey Y; Selzle, Heinrich L; Cloke, F Geoffrey N; Markin, Gennady V; Shevelev, Yury A; Domrachev, Georgy A; Schlag, Edward W

2010-10-28

For over 25 years zero kinetic energy (ZEKE) spectroscopy has yielded a rich foundation of high-resolution results of molecular ions. This was based on the discovery in the late 60's of long-lived ion states throughout the ionization continuum of molecular ions. Here, an example is chosen from another fundamental system pioneered at this university. The mass-analyzed threshold ionization (MATI) spectra of jet-cooled chromium bisarene complexes (η(6)-RPh)(2)Cr (R = Me (1), Et (2), i-Pr (3), and t-Bu (4)) have been measured and interpreted on the basis of DFT calculations. The MATI spectra of complexes 1 and 2 appear to reveal features arising from ionizations of the isomers formed by the rotation of one arene ring relative to the other. The 1 and 2 MATI spectra show two intense peaks corresponding to the 0(0)(0) ionizations with inverse intensity ratios. As indicated by the DFT calculations, the intensity ratio change on going from 1 to 2 results from different isomers contributing to each MATI peak. The ionization energies corresponding to the 0(0)(0) peaks are 42746 ± 5 and 42809 ± 5 cm(-1) for compound 1 and 42379 ± 5 and 42463 ± 5 cm(-1) for complex 2. The 1 and 2 spectra show also the weaker features representing transitions to the vibrationally excited cationic levels, the signals of individual rotamers being detected and assigned on the basis of calculated vibrational frequencies. The MATI spectra of compounds 3 and 4 reveal only one strong peak because of close ionization potentials of the isomers contributing to the MATI signal. The 3 and 4 ionization energies are 42104 ± 5 and 41917 ± 5 cm(-1), respectively. The precise values of ionization energies obtained from the MATI spectra reveal a nonlinear dependence of the IE on the number of Me groups in the alkyl substituents of (η(6)-RPh)(2)Cr. This can be explained by an increase in the molecular zero point energies on methylation of the substituents.

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

Verma, Prakash; Bartlett, Rodney J., E-mail: bartlett@qtp.ufl.edu

Core excitation energies are computed with time-dependent density functional theory (TD-DFT) using the ionization energy corrected exchange and correlation potential QTP(0,0). QTP(0,0) provides C, N, and O K-edge spectra to about an electron volt. A mean absolute error (MAE) of 0.77 and a maximum error of 2.6 eV is observed for QTP(0,0) for many small molecules. TD-DFT based on QTP (0,0) is then used to describe the core-excitation spectra of the 22 amino acids. TD-DFT with conventional functionals greatly underestimates core excitation energies, largely due to the significant error in the Kohn-Sham occupied eigenvalues. To the contrary, the ionization energymore » corrected potential, QTP(0,0), provides excellent approximations (MAE of 0.53 eV) for core ionization energies as eigenvalues of the Kohn-Sham equations. As a consequence, core excitation energies are accurately described with QTP(0,0), as are the core ionization energies important in X-ray photoionization spectra or electron spectroscopy for chemical analysis.« less

Time- and dose-dependent effects of total-body ionizing radiation on muscle stem cells

PubMed Central

Masuda, Shinya; Hisamatsu, Tsubasa; Seko, Daiki; Urata, Yoshishige; Goto, Shinji; Li, Tao-Sheng; Ono, Yusuke

2015-01-01

Exposure to high levels of genotoxic stress, such as high-dose ionizing radiation, increases both cancer and noncancer risks. However, it remains debatable whether low-dose ionizing radiation reduces cellular function, or rather induces hormetic health benefits. Here, we investigated the effects of total-body γ-ray radiation on muscle stem cells, called satellite cells. Adult C57BL/6 mice were exposed to γ-radiation at low- to high-dose rates (low, 2 or 10 mGy/day; moderate, 50 mGy/day; high, 250 mGy/day) for 30 days. No hormetic responses in proliferation, differentiation, or self-renewal of satellite cells were observed in low-dose radiation-exposed mice at the acute phase. However, at the chronic phase, population expansion of satellite cell-derived progeny was slightly decreased in mice exposed to low-dose radiation. Taken together, low-dose ionizing irradiation may suppress satellite cell function, rather than induce hormetic health benefits, in skeletal muscle in adult mice. PMID:25869487

The great importance of normalization of LC-MS data for highly-accurate non-targeted metabolomics.

PubMed

Mizuno, Hajime; Ueda, Kazuki; Kobayashi, Yuta; Tsuyama, Naohiro; Todoroki, Kenichiro; Min, Jun Zhe; Toyo'oka, Toshimasa

2017-01-01

The non-targeted metabolomics analysis of biological samples is very important to understand biological functions and diseases. LC combined with electrospray ionization-based MS has been a powerful tool and widely used for metabolomic analyses. However, the ionization efficiency of electrospray ionization fluctuates for various unexpected reasons such as matrix effects and intraday variations of the instrument performances. To remove these fluctuations, normalization methods have been developed. Such techniques include increasing the sensitivity, separating co-eluting components and normalizing the ionization efficiencies. Normalization techniques allow simultaneously correcting of the ionization efficiencies of the detected metabolite peaks and achieving quantitative non-targeted metabolomics. In this review paper, we focused on these normalization methods for non-targeted metabolomics by LC-MS. Copyright © 2016 John Wiley & Sons, Ltd.

Population kinetics on K alpha lines of partially ionized Cl atoms.

PubMed

Kawamura, Tohru; Nishimura, Hiroaki; Koike, Fumihiro; Ochi, Yoshihiro; Matsui, Ryoji; Miao, Wen Yong; Okihara, Shinichiro; Sakabe, Shuji; Uschmann, Ingo; Förster, Eckhart; Mima, Kunioki

2002-07-01

A population kinetics code was developed to analyze K alpha emission from partially ionized chlorine atoms in hydrocarbon plasmas. Atomic processes are solved under collisional-radiative equilibrium for two-temperature plasmas. It is shown that the fast electrons dominantly contribute to ionize the K-shell bound electrons (i.e., inner-shell ionization) and the cold electrons to the outer-shell bound ones. Ratios of K alpha lines of partially ionized atoms are presented as a function of cold-electron temperature. The model was validated by observation of the K alpha lines from a chlorinated plastic target irradiated with 1 TW Ti:sapphire laser pulses at 1.5 x 10(17) W/cm(2), inferring a plasma temperature of about 100 eV on the target surface.

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

NASA Technical Reports Server (NTRS)

Leibowitz, L. P.

1972-01-01

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

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

NASA Technical Reports Server (NTRS)

Leibowitz, L. P.

1973-01-01

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

Sequential and direct ionic excitation in the strong-field ionization of 1-butene molecules.

PubMed

Schell, Felix; Boguslavskiy, Andrey E; Schulz, Claus Peter; Patchkovskii, Serguei; Vrakking, Marc J J; Stolow, Albert; Mikosch, Jochen

2018-05-18

We study the Strong-Field Ionization (SFI) of the hydrocarbon 1-butene as a function of wavelength using photoion-photoelectron covariance and coincidence spectroscopy. We observe a striking transition in the fragment-associated photoelectron spectra: from a single Above Threshold Ionization (ATI) progression for photon energies less than the cation D0-D1 gap to two ATI progressions for a photon energy greater than this gap. For the first case, electronically excited cations are created by SFI populating the ground cationic state D0, followed by sequential post-ionization excitation. For the second case, direct sub-cycle SFI to the D1 excited cation state contributes significantly. Our experiments access ionization dynamics in a regime where strong-field and resonance-enhanced processes can interplay.

Derivation of ionization balance for calcium XVIII/XIX using XRP solar X-ray data

NASA Astrophysics Data System (ADS)

Antonucci, E.; Gabriel, A. H.; Doyle, J. G.; Dubau, J.; Faucher, P.; Jordan, C.; Veck, N.

1984-04-01

Spectra of calcium from solar flares are used in an attempt to derive an ionization balance for Ca XVIII/Ca XIX. The isothermal assumption inherent in this derivation is shown not to introduce errors, by modelling a number of hypothetical nonisothermal plasmas. The unresolved blend of calcium and argon lines prevents a definitive determination of the results, owing to uncertainties in the ratio of abundances of these elements. The resulting ionization balance curves are presented as a function of the solar argon/calcium abundance ratio. The theoretical ionization balance of Doyle and Raymond is consistent with the data. To within the expected accuracy of the atomic theories, there is no reason to assume that the flare plasma is other than close to steady-state ionization balance.

Agreement of Experiment and Theory on the Single Ionization of Helium by Fast Proton Impact.

PubMed

Gassert, H; Chuluunbaatar, O; Waitz, M; Trinter, F; Kim, H-K; Bauer, T; Laucke, A; Müller, Ch; Voigtsberger, J; Weller, M; Rist, J; Pitzer, M; Zeller, S; Jahnke, T; Schmidt, L Ph H; Williams, J B; Zaytsev, S A; Bulychev, A A; Kouzakov, K A; Schmidt-Böcking, H; Dörner, R; Popov, Yu V; Schöffler, M S

2016-02-19

Even though the study of ion-atom collisions is a mature field of atomic physics, large discrepancies between experiment and theoretical calculations are still common. Here we present experimental results with high momentum resolution on the single ionization of helium induced by 1-MeV protons, and we compare these to theoretical calculations. The overall agreement is strikingly good, and even the first Born approximation yields good agreement between theory and experiment. This has been expected for several decades, but so far has not been accomplished. The influence of projectile coherence effects on the measured data is briefly discussed in terms of an ongoing dispute on the existence of nodal structures in the electron angular emission distributions.

Optimization of carrier multiplication for more effcient solar cells: the case of Sn quantum dots.

PubMed

Allan, Guy; Delerue, Christophe

2011-09-27

We present calculations of impact ionization rates, carrier multiplication yields, and solar-power conversion efficiencies in solar cells based on quantum dots (QDs) of a semimetal, α-Sn. Using these results and previous ones on PbSe and PbS QDs, we discuss a strategy to select QDs with the highest carrier multiplication rate for more efficient solar cells. We suggest using QDs of materials with a close to zero band gap and a high multiplicity of the bands in order to favor the relaxation of photoexcited carriers by impact ionization. Even in that case, the improvement of the maximum solar-power conversion efficiency appears to be a challenging task. © 2011 American Chemical Society

Self-assembly of Metallamacrocycles Employing a New Benzil-based Organometallic Bisplatinum(II) Acceptor.

PubMed

Roy, Bijan; Shanmugaraju, Sankarasekaran; Saha, Rupak; Mukherjee, Partha Sarathi

2015-01-01

A benzil-based semi-rigid dinuclear-organometallic acceptor 4,4'-bis[trans-Pt(PEt(3))(2)(NO(3))(ethynyl)]benzil (bisPt-NO(3)) containing a Pt-ethynyl functionality was synthesized in good yield and characterized by multinuclear NMR ((1)H, (31)P, and (13)C), electrospray ionization mass spectrometry (ESI-MS), and single-crystal X-ray diffraction analysis of the iodide analogue bisPt-I. The stoichiometric (1:1) combination of the acceptor bisPt-NO(3) separately with four different ditopic donors (L(1)-L(4); L(1) = 9-ethyl-3,6-di(1H-imidazol-1-yl)-9H-carbazole, L(2) = 1,4-bis((1H-imidazol-1-yl)methyl)benzene, L(3) = 1,3-bis((1H-imidazol-1-yl)methyl)benzene and L(4) = 9,10-bis((1H-imidazol-1-yl) methyl)anthracene) yielded four [2 + 2] self-assembled metallacycles M(1)-M(4) in quantitative yields, respectively. All these newly synthesized assemblies were characterized by various spectroscopic techniques (NMR, IR, ESI-MS) and their sizes/shapes were predicted through geometry optimization employing the PM6 semi-empirical method. The benzil moiety was introduced in the backbone of the acceptor bisPt-NO(3) due to the interesting structural feature of long carbonyl C-C bond (∼1.54 Å), which enabled us to probe the role of conformational flexibility on size and shapes of the resulting coordination ensembles.

Gold nanoparticles and their alternatives for radiation therapy enhancement

PubMed Central

Cooper, Daniel R.; Bekah, Devesh; Nadeau, Jay L.

2014-01-01

Radiation therapy is one of the most commonly used treatments for cancer. The dose of delivered ionizing radiation can be amplified by the presence of high-Z materials via an enhancement of the photoelectric effect; the most widely studied material is gold (atomic number 79). However, a large amount is needed to obtain a significant dose enhancement, presenting a challenge for delivery. In order to make this technique of broader applicability, the gold must be targeted, or alternative formulations developed that do not rely solely on the photoelectric effect. One possible approach is to excite scintillating nanoparticles with ionizing radiation, and then exploit energy transfer between these particles and attached dyes in a manner analogous to photodynamic therapy (PDT). Doped rare-earth halides and semiconductor quantum dots have been investigated for this purpose. However, although the spectrum of emitted light after radiation excitation is usually similar to that seen with light excitation, the yield is not. Measurement of scintillation yields is challenging, and in many cases has been done only for bulk materials, with little understanding of how the principles translate to the nanoscale. Another alternative is to use local heating using gold or iron, followed by application of ionizing radiation. Hyperthermia pre-sensitizes the tumors, leading to an improved response. Another approach is to use chemotherapeutic drugs that can radiosensitize tumors. Drugs may be attached to high-Z nanoparticles or encapsulated. This article discusses each of these techniques, giving an overview of the current state of nanoparticle-assisted radiation therapy and future directions. PMID:25353018

Rejoining and misrejoining of radiation-induced chromatin breaks. IV. Charged particles

NASA Technical Reports Server (NTRS)

Durante, M.; Furusawa, Y.; George, K.; Gialanella, G.; Greco, O.; Grossi, G.; Matsufuji, N.; Pugliese, M.; Yang, T. C.

1998-01-01

We have recently reported the kinetics of chromosome rejoining and exchange formation in human lymphocytes exposed to gamma rays using the techniques of fluorescence in situ hybridization (FISH) and premature chromosome condensation (PCC). In this paper, we have extended previous measurements to cells exposed to charged particles. Our goal was to determine differences in chromatin break rejoining and misrejoining after exposure to low- and high-linear energy transfer (LET) radiation. Cells were irradiated with hydrogen, neon, carbon or iron ions in the LET range 0.3-140 keV/microm and were incubated at 37 degrees C for various times after exposure. Little difference was observed in the yield of early prematurely condensed chromosome breaks for the different ions. The kinetics of break rejoining was exponential for all ions and had similar time constants, but the residual level of unrejoined breaks after prolonged incubation was higher for high-LET radiation. The kinetics of exchange formation was also similar for the different ions, but the yield of chromosome interchanges measured soon after exposure was higher for high-LET particles, suggesting that a higher fraction of DNA breaks are misrejoined quickly. On the other hand, the rate of formation of complete exchanges was slightly lower for densely ionizing radiation. The ratios between the yields of different types of aberrations observed at 10 h postirradiation in prematurely condensed chromosome preparations were dependent on LET. We found significant differences between the yields of aberrations measured in interphase (after repair) and metaphase for densely ionizing radiation. This difference might be caused by prolonged mitotic delay and/or interphase death. Overall, the results point out significant differences between low- and high-LET radiation for the formation of chromosome aberrations.

Role of isolated and clustered DNA damage and the post-irradiating repair process in the effects of heavy ion beam irradiation.

PubMed

Tokuyama, Yuka; Furusawa, Yoshiya; Ide, Hiroshi; Yasui, Akira; Terato, Hiroaki

2015-05-01

Clustered DNA damage is a specific type of DNA damage induced by ionizing radiation. Any type of ionizing radiation traverses the target DNA molecule as a beam, inducing damage along its track. Our previous study showed that clustered DNA damage yields decreased with increased linear energy transfer (LET), leading us to investigate the importance of clustered DNA damage in the biological effects of heavy ion beam radiation. In this study, we analyzed the yield of clustered base damage (comprising multiple base lesions) in cultured cells irradiated with various heavy ion beams, and investigated isolated base damage and the repair process in post-irradiation cultured cells. Chinese hamster ovary (CHO) cells were irradiated by carbon, silicon, argon and iron ion beams with LETs of 13, 55, 90 and 200 keV µm(-1), respectively. Agarose gel electrophoresis of the cells with enzymatic treatments indicated that clustered base damage yields decreased as the LET increased. The aldehyde reactive probe procedure showed that isolated base damage yields in the irradiated cells followed the same pattern. To analyze the cellular base damage process, clustered DNA damage repair was investigated using DNA repair mutant cells. DNA double-strand breaks accumulated in CHO mutant cells lacking Xrcc1 after irradiation, and the cell viability decreased. On the other hand, mouse embryonic fibroblast (Mef) cells lacking both Nth1 and Ogg1 became more resistant than the wild type Mef. Thus, clustered base damage seems to be involved in the expression of heavy ion beam biological effects via the repair process. © The Author 2015. Published by Oxford University Press on behalf of The Japan Radiation Research Society and Japanese Society for Radiation Oncology.

Structure factors for tunneling ionization rates of molecules: General Hartree-Fock-based integral representation

NASA Astrophysics Data System (ADS)

Madsen, Lars Bojer; Jensen, Frank; Dnestryan, Andrey I.; Tolstikhin, Oleg I.

2017-07-01

In the leading-order approximation of the weak-field asymptotic theory (WFAT), the dependence of the tunneling ionization rate of a molecule in an electric field on its orientation with respect to the field is determined by the structure factor of the ionizing molecular orbital. The WFAT yields an expression for the structure factor in terms of a local property of the orbital in the asymptotic region. However, in general quantum chemistry approaches molecular orbitals are expanded in a Gaussian basis which does not reproduce their asymptotic behavior correctly. This hinders the application of the WFAT to polyatomic molecules, which are attracting increasing interest in strong-field physics. Recently, an integral-equation approach to the WFAT for tunneling ionization of one electron from an arbitrary potential has been developed. The structure factor is expressed in an integral form as a matrix element involving the ionizing orbital. The integral is not sensitive to the asymptotic behavior of the orbital, which resolves the difficulty mentioned above. Here, we extend the integral representation for the structure factor to many-electron systems treated within the Hartree-Fock method and show how it can be implemented on the basis of standard quantum chemistry software packages. We validate the methodology by considering noble-gas atoms and the CO molecule, for which accurate structure factors exist in the literature. We also present benchmark results for CO2 and for NH3 in the pyramidal and planar geometries.

Accuracy of theory for calculating electron impact ionization of molecules

NASA Astrophysics Data System (ADS)

Chaluvadi, Hari Hara Kumar

The study of electron impact single ionization of atoms and molecules has provided valuable information about fundamental collisions. The most detailed information is obtained from triple differential cross sections (TDCS) in which the energy and momentum of all three final state particles are determined. These cross sections are much more difficult for theory since the detailed kinematics of the experiment become important. There are many theoretical approximations for ionization of molecules. One of the successful methods is the molecular 3-body distorted wave (M3DW) approximation. One of the strengths of the DW approximation is that it can be applied for any energy and any size molecule. One of the approximations that has been made to significantly reduce the required computer time is the OAMO (orientation averaged molecular orbital) approximation. In this dissertation, the accuracy of the M3DW-OAMO is tested for different molecules. Surprisingly, the M3DW-OAMO approximation yields reasonably good agreement with experiment for ionization of H2 and N2. On the other hand, the M3DW-OAMO results for ionization of CH4, NH3 and DNA derivative molecules did not agree very well with experiment. Consequently, we proposed the M3DW with a proper average (PA) calculation. In this dissertation, it is shown that the M3DW-PA calculations for CH4 and SF6 are in much better agreement with experimental data than the M3DW-OAMO results.

Curvature dependence of the effect of ionic functionalization on the attraction among nanoparticles in dispersion

NASA Astrophysics Data System (ADS)

Jabes, B. Shadrack; Bratko, Dusan; Luzar, Alenka

2018-06-01

Solubilization of nanoparticles facilitates nanomaterial processing and enables new applications. An effective method to improve dispersibility in water is provided by ionic functionalization. We explore how the necessary extent of functionalization depends on the particle geometry. Using molecular dynamics/umbrella sampling simulations, we determine the effect of the solute curvature on solvent-averaged interactions among ionizing graphitic nanoparticles in aqueous dispersion. We tune the hydrophilicity of molecular-brush coated fullerenes, carbon nanotubes, and graphane platelets by gradually replacing a fraction of the methyl end groups of the alkyl coating by the ionizing -COOK or -NH3Cl groups. To assess the change in nanoparticles' dispersibility in water, we determine the potential-of-mean-force profiles at varied degrees of ionization. When the coating comprises only propyl groups, the attraction between the hydrophobic particles intensifies from spherical to cylindrical to planar geometry. This is explained by the increasing fraction of surface groups that can be brought into contact and the reduced access to water molecules, both following the above sequence. When ionic groups are added, however, the dispersibility increases in the opposite order, with the biggest effect in the planar geometry and the smallest in the spherical geometry. These results highlight the important role of geometry in nanoparticle solubilization by ionic functionalities, with about twice higher threshold surface charge necessary to stabilize a dispersion of spherical than planar particles. At 25%-50% ionization, the potential of mean force reaches a plateau because of the counterion condensation and saturated brush hydration. Moreover, the increase in the fraction of ionic groups can weaken the repulsion through counterion correlations between adjacent nanoparticles. High degrees of ionization and concomitant ionic screening gradually reduce the differences among surface interactions in distinct geometries until an essentially curvature-independent dispersion environment is created. Insights into tuning nanoparticle interactions can guide the synthesis of a broad class of nonpolar nanoparticles, where solubility is achieved by ionic functionalization.

CHILI – the Chicago Instrument for Laser Ionization – a new tool for isotope measurements in cosmochemistry

DOE PAGES

Stephan, Thomas; Trappitsch, Reto; Davis, Andrew M.; ...

2016-06-17

Here, we describe CHILI, the Chicago Instrument for Laser Ionization, a new resonance ionization mass spectrometer developed for isotopic analysis at high spatial resolution and high sensitivity of small samples like contemporary interstellar dust grains returned by the Stardust spacecraft. We explain how CHILI addresses the technical challenges associated with such analyses by pushing most technical specifications towards their physical limits. As an initial demonstration, after many years of designing and developing CHILI, we have analyzed presolar silicon carbide grains for their isotopic compositions of strontium, zirconium, and barium. Subsequently, after further technical improvements, we have used CHILI to analyze,more » for the first time without interference, all stable isotopes of iron and nickel simultaneously in presolar silicon carbide grains. With a special timing scheme for the ionization lasers, we separated iron and nickel isotopes in the time-of-flight spectrum such that the isobaric interference between 58Fe and 58Ni was resolved. In-depth discussion of the astrophysical implications of the presolar grain results is deferred to dedicated later publications. Here we focus on the technical aspects of CHILI, its status quo, and further developments necessary to achieve CHILI’s ultimate goals, 10 nm lateral resolution and 30–40% useful yield.« less

Non-ideal magnetohydrodynamic simulations of the two-stage fragmentation model for cluster formation

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

Bailey, Nicole D.; Basu, Shantanu, E-mail: N.Bailey@leeds.ac.uk, E-mail: basu@uwo.ca

2014-01-01

We model molecular cloud fragmentation with thin-disk, non-ideal magnetohydrodynamic simulations that include ambipolar diffusion and partial ionization that transitions from primarily ultraviolet-dominated to cosmic-ray-dominated regimes. These simulations are used to determine the conditions required for star clusters to form through a two-stage fragmentation scenario. Recent linear analyses have shown that the fragmentation length scales and timescales can undergo a dramatic drop across the column density boundary that separates the ultraviolet- and cosmic-ray-dominated ionization regimes. As found in earlier studies, the absence of an ionization drop and regular perturbations leads to a single-stage fragmentation on pc scales in transcritical clouds, somore » that the nonlinear evolution yields the same fragment sizes as predicted by linear theory. However, we find that a combination of initial transcritical mass-to-flux ratio, evolution through a column density regime in which the ionization drop takes place, and regular small perturbations to the mass-to-flux ratio is sufficient to cause a second stage of fragmentation during the nonlinear evolution. Cores of size ∼0.1 pc are formed within an initial fragment of ∼pc size. Regular perturbations to the mass-to-flux ratio also accelerate the onset of runaway collapse.« less

Identification of doubly excited states in nonsequential double ionization of Ar in strong laser fields

NASA Astrophysics Data System (ADS)

Chen, Zhangjin; Li, Xiaojin; Sun, Xiaoli; Hao, Xiaolei; Chen, Jing

2017-12-01

We use the semiclassical model to study the intensity dependence of nonsequential double ionization (NSDI) of Ar in short strong laser pulses. The contributions to NSDI through sequential ionization of doubly excited states (SIDE) are identified by tracking the energy trajectories of the two outgoing electrons. The correlated electron momentum distributions are calculated from which the longitudinal momentum distributions of the fast and the slow electrons for the side-by-side and the back-to-back emissions are obtained. The simulated momentum distributions of the fast and the slow electrons for NSDI of Ar by linearly polarized fields with a wavelength of 795 nm at an intensity of 7 × 1013 W cm-2 are in good agreement with the experimental measurements of Liu et al (2014 Phys. Rev. Lett. 112 013003). We demonstrate that the process of double ionization through SIDE dominates NSDI only when the laser intensities are below the recollision threshold; nevertheless, for higher intensities the SIDE process still takes place although the contribution to the NSDI yields decreases rapidly as the intensity increases. It has been found that for SIDE at different intensities, both the correlated electron momentum spectra and the momentum distributions of the fast and the slow electrons remain the same.

CHILI – the Chicago Instrument for Laser Ionization – a new tool for isotope measurements in cosmochemistry

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

Stephan, Thomas; Trappitsch, Reto; Davis, Andrew M.

2016-08-01

We describe CHILI, the Chicago Instrument for Laser Ionization, a new resonance ionization mass spectrometer developed for isotopic analysis at high spatial resolution and high sensitivity of small samples like contemporary interstellar dust grains returned by the Stardust spacecraft. We explain how CHILI addresses the technical challenges associated with such analyses by pushing most technical specifications towards their physical limits. As an initial demonstration, after many years of designing and developing CHILI, we have analyzed presolar silicon carbide grains for their isotopic compositions of strontium, zirconium, and barium. Subsequently, after further technical improvements, we have used CHILI to analyze, formore » the first time without interference, all stable isotopes of iron and nickel simultaneously in presolar silicon carbide grains. With a special timing scheme for the ionization lasers, we separated iron and nickel isotopes in the time-of-flight spectrum such that the isobaric interference between Fe-58 and Ni-58 was resolved. In-depth discussion of the astrophysical implications of the presolar grain results is deferred to dedicated later publications. Here we focus on the technical aspects of CHILI, its status quo, and further developments necessary to achieve CHILI's ultimate goals, similar to 10 nm lateral resolution and 30-40% useful yield.« less

Quantum interference in laser-induced nonsequential double ionization

NASA Astrophysics Data System (ADS)

Quan, Wei; Hao, XiaoLei; Wang, YanLan; Chen, YongJu; Yu, ShaoGang; Xu, SongPo; Xiao, ZhiLei; Sun, RenPing; Lai, XuanYang; Hu, ShiLin; Liu, MingQing; Shu, Zheng; Wang, XiaoDong; Li, WeiDong; Becker, Wilhelm; Liu, XiaoJun; Chen, Jing

2017-09-01

Quantum interference plays an important role in various intense-laser-driven atomic phenomena, e.g., above-threshold ionization and high-order-harmonic generation, and provides a useful tool in ultrafast imaging of atomic and molecular structure and dynamics. However, it has eluded observation in nonsequential double ionization (NSDI), which serves as an ideal prototype to study electron-electron correlation. Thus far, NSDI usually could be well understood from a semiclassical perspective, where all quantum aspects have been ignored after the first electron has tunneled. Here we perform coincidence measurements for NSDI of xenon subject to laser pulses at 2400 nm. It is found that the intensity dependence of the asymmetry parameter between the yields in the second and fourth quadrants and those in the first and third quadrants of the electron-momentum-correlation distributions exhibits a peculiar fast oscillatory structure, which is beyond the scope of the semiclassical picture. Our theoretical analysis indicates that this oscillation can be attributed to interference between the contributions of different excited states in the recollision-excitation-with-subsequent-ionization channel. Our work demonstrates the significant role of quantum interference in NSDI and may create an additional pathway towards manipulation and imaging of the ultrafast atomic and molecular dynamics in intense laser fields.

Novel model of negative secondary ion formation and its use to refine the electronegativity of almost fifty elements.

PubMed

Wittmaack, Klaus

2014-06-17

This study aimed to examine the recently proposed idea that the ionic contribution to atomic bonds is essential in determining the charge state of sputtered atoms. Use was made of negative secondary ion yields reported by Wilson for a large number of elements implanted in silicon and then sputter profiled by Cs bombardment. The derived normalized ion yields (or fractions) P vary by 6 orders of magnitude, but the expected exponential dependence on the electron affinity EA is evident only vaguely. Remarkably, a correlation of similar quality is observed if the data are presented as a function of the ionization potential IP. With IP being the dominant (if not sole) contributor to the electronegativity χ, one is led to assume that P depends on the sum χ + EA. About 72% of the "nonsaturated" ion yields are in accordance with a dependence of the form P ∝ exp[(χ + EA)/ε], with ε ≅ 0.2 eV, provided the appropriate value of χ is selected from the electronegativity tables of Pauling (read in eV), Mulliken or Allen. However, each of the three sources contributes only about one-third to the favorable electronegativity data. This unsatisfactory situation initiated the idea to derive the "true" electronegativity χSIMS from the measured ion yields P(χ + EA), verified for 48 elements. Significant negative deviations of χSIMS from a smooth increase with increasing atomic number are evident for elements with special outer-shell electron configurations such as (n-1)d(g-1)ns(1) or (n-1)d(10)ns(2)np(1). The results strongly support the new model of secondary ion formation and provide means for refining electronegativity data.

Exploring matrix effects and quantifying organic additives in hydraulic fracturing associated fluids using liquid chromatography electrospray ionization mass spectrometry.

PubMed

Nell, Marika; Helbling, Damian E

2018-05-23

Hydraulic fracturing (HF) operations utilize millions of gallons of water amended with chemical additives including biocides, corrosion inhibitors, and surfactants. Fluids injected into the subsurface return to the surface as wastewaters, which contain a complex mixture of additives, transformation products, and geogenic chemical constituents. Quantitative analytical methods are needed to evaluate wastewater disposal alternatives or to conduct adequate exposure assessments. However, our narrow understanding of how matrix effects change the ionization efficiency of target analytes limits the quantitative analysis of polar to semi-polar HF additives by means of liquid chromatography electrospray ionization mass spectrometry (LC-ESI-MS). To address this limitation, we explored the ways in which matrix chemistry influences the ionization of seventeen priority HF additives with a modified standard addition approach. We then used the data to quantify HF additives in HF-associated fluids. Our results demonstrate that HF additives generally exhibit suppressed ionization in HF-associated fluids, though HF additives that predominantly form sodiated adducts exhibit significantly enhanced ionization in produced water samples, which is largely the result of adduct shifting. In a preliminary screening, we identified glutaraldehyde and 2-butoxyethanol along with homologues of benzalkonium chloride (ADBAC), polyethylene glycol (PEG), and polypropylene glycol (PPG) in HF-associated fluids. We then used matrix recovery factors to provide the first quantitative measurements of individual homologues of ADBAC, PEG, and PPG in HF-associated fluids ranging from mg L-1 levels in hydraulic fracturing fluid to low μg L-1 levels in PW samples. Our approach is generalizable across sample types and shale formations and yields important data to evaluate wastewater disposal alternatives or implement exposure assessments.

Spectroscopy of the UO+2 cation and the delayed ionization of UO2.

PubMed

Merritt, Jeremy M; Han, Jiande; Heaven, Michael C

2008-02-28

Vibronically resolved spectra for the UO+2 cation have been recorded using the pulsed field ionization zero electron kinetic energy (PFI-ZEKE) technique. For the ground state, long progressions in both the bending and symmetric stretch vibrations were observed. Bend and stretch progressions of the first electronically excited state were also observed, and the origin was found at an energy of 2678 cm(-1) above the ground state zero-point level. This observation is consistent with a recent theoretical prediction [Infante et al., J. Chem. Phys. 127, 124308 (2007)]. The ionization energy for UO2, derived from the PFI-ZEKE spectrum, namely, 6.127(1) eV, is in excellent agreement with the value obtained from an earlier photoionization efficiency measurement. Delayed ionization of UO2 in the gas phase has been reported previously [Han et al., J. Chem. Phys. 120, 5155 (2004)]. Here, we extend the characterization of the delayed ionization process by performing a quantitative study of the ionization rate as a function of the energy above the ionization threshold. The ionization rate was found to be 5 x 10(6) s(-1) at threshold, and increased linearly with increasing energy in the range investigated (0-1200 cm(-1)).

Valence ionized states of iron pentacarbonyl and eta5-cyclopentadienyl cobalt dicarbonyl studied by symmetry-adapted cluster-configuration interaction calculation and collision-energy resolved Penning ionization electron spectroscopy.

PubMed

Fukuda, Ryoichi; Ehara, Masahiro; Nakatsuji, Hiroshi; Kishimoto, Naoki; Ohno, Koichi

2010-02-28

Valence ionized states of iron pentacarbonyl Fe(CO)(5) and eta(5)-cyclopentadienyl cobalt dicarbonyl Co(eta(5)-C(5)H(5))(CO)(2) have been studied by ultraviolet photoelectron spectroscopy, two-dimensional Penning ionization electron spectroscopy (2D-PIES), and symmetry-adapted cluster-configuration interaction calculations. Theory provided reliable assignments for the complex ionization spectra of these molecules, which have metal-carbonyl bonds. Theoretical ionization energies agreed well with experimental observations and the calculated wave functions could explain the relative intensities of PIES spectra. The collision-energy dependence of partial ionization cross sections (CEDPICS) was obtained by 2D-PIES. To interpret these CEDPICS, the interaction potentials between the molecules and a Li atom were examined in several coordinates by calculations. The relation between the slope of the CEDPICS and the electronic structure of the ionized states, such as molecular symmetry and the spatial distribution of ionizing orbitals, was analyzed. In Fe(CO)(5), an attractive interaction was obtained for the equatorial CO, while the interaction for the axial CO direction was repulsive. For Co(eta(5)-C(5)H(5))(CO)(2), the interaction potential in the direction of both Co-C-O and Co-Cp ring was attractive. These anisotropic interactions and ionizing orbital distributions consistently explain the relative slopes of the CEDPICS.

Influence of ionizing radiation on the immune response

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

Brocadeszaalberg, O.

1974-01-01

The effects of ionizing radiation on the immune response are reviewed. Following an introduction on the function of the immune apparatus, the effect of radiation in the different cell types of the immune system is described. The possible consequences of these effects on the prognosis of radiation victims are discussed. (GRA)

Ramsey-type spectroscopy in the XUV spectral region

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

Pirri, A.; European Laboratory for Nonlinear Spectroscopy, Via N. Carrara 1, I-50019 Sesto Fiorentino; Sali, E.

2010-02-02

We report an experimental and theoretical investigation of Ramsey-type spectroscopy with high-order harmonic generation applied to autoionizing states of Krypton. The ionization yield, detected by an ion-mass spectrometer, shows the characteristic quantum interference pattern. The behaviour of the fringe contrast was interpreted on the basis of a simple analytic model, which reproduces the experimental data without any free parameter.

Quantum statistical mechanics of dense partially ionized hydrogen.

NASA Technical Reports Server (NTRS)

Dewitt, H. E.; Rogers, F. J.

1972-01-01

The theory of dense hydrogenic plasmas beginning with the two component quantum grand partition function is reviewed. It is shown that ionization equilibrium and molecular dissociation equilibrium can be treated in the same manner with proper consideration of all two-body states. A quantum perturbation expansion is used to give an accurate calculation of the equation of state of the gas for any degree of dissociation and ionization. In this theory, the effective interaction between any two charges is the dynamic screened potential obtained from the plasma dielectric function. We make the static approximation; and we carry out detailed numerical calculations with the bound and scattering states of the Debye potential, using the Beth-Uhlenbeck form of the quantum second virial coefficient. We compare our results with calculations from the Saha equation.

New diagnostic methods for laser plasma- and microwave-enhanced combustion

PubMed Central

Miles, Richard B; Michael, James B; Limbach, Christopher M; McGuire, Sean D; Chng, Tat Loon; Edwards, Matthew R; DeLuca, Nicholas J; Shneider, Mikhail N; Dogariu, Arthur

2015-01-01

The study of pulsed laser- and microwave-induced plasma interactions with atmospheric and higher pressure combusting gases requires rapid diagnostic methods that are capable of determining the mechanisms by which these interactions are taking place. New rapid diagnostics are presented here extending the capabilities of Rayleigh and Thomson scattering and resonance-enhanced multi-photon ionization (REMPI) detection and introducing femtosecond laser-induced velocity and temperature profile imaging. Spectrally filtered Rayleigh scattering provides a method for the planar imaging of temperature fields for constant pressure interactions and line imaging of velocity, temperature and density profiles. Depolarization of Rayleigh scattering provides a measure of the dissociation fraction, and multi-wavelength line imaging enables the separation of Thomson scattering from Rayleigh scattering. Radar REMPI takes advantage of high-frequency microwave scattering from the region of laser-selected species ionization to extend REMPI to atmospheric pressures and implement it as a stand-off detection method for atomic and molecular species in combusting environments. Femtosecond laser electronic excitation tagging (FLEET) generates highly excited molecular species and dissociation through the focal zone of the laser. The prompt fluorescence from excited molecular species yields temperature profiles, and the delayed fluorescence from recombining atomic fragments yields velocity profiles. PMID:26170432

Nonadiabatic Dynamics May Be Probed through Electronic Coherence in Time-Resolved Photoelectron Spectroscopy.

PubMed

Bennett, Kochise; Kowalewski, Markus; Mukamel, Shaul

2016-02-09

We present a hierarchy of Fermi golden rules (FGRs) that incorporate strongly coupled electronic/nuclear dynamics in time-resolved photoelectron spectroscopy (TRPES) signals at different levels of theory. Expansion in the joint electronic and nuclear eigenbasis yields the numerically most challenging exact FGR (eFGR). The quasistatic Fermi Golden Rule (qsFGR) neglects nuclear motion during the photoionization process but takes into account electronic coherences as well as populations initially present in the pumped matter as well as those generated internally by coupling between electronic surfaces. The standard semiclassical Fermi Golden Rule (scFGR) neglects the electronic coherences and the nuclear kinetic energy during the ionizing pulse altogether, yielding the classical Condon approximation. The coherence contributions depend on the phase-profile of the ionizing field, allowing coherent control of TRPES signals. The photoelectron spectrum from model systems is simulated using these three levels of theory. The eFGR and the qsFGR show temporal oscillations originating from the electronic or vibrational coherences generated as the nuclear wave packet traverses a conical intersection. These oscillations, which are missed by the scFGR, directly reveal the time-evolving splitting between electronic states of the neutral molecule in the curve-crossing regime.

Sensitive and Structure-Informative N-Glycosylation Analysis by MALDI-MS; Ionization, Fragmentation, and Derivatization

PubMed Central

Nishikaze, Takashi

2017-01-01

Mass spectrometry (MS) has become an indispensable tool for analyzing post translational modifications of proteins, including N-glycosylated molecules. Because most glycosylation sites carry a multitude of glycans, referred to as “glycoforms,” the purpose of an N-glycosylation analysis is glycoform profiling and glycosylation site mapping. Matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) has unique characteristics that are suited for the sensitive analysis of N-glycosylated products. However, the analysis is often hampered by the inherent physico-chemical properties of N-glycans. Glycans are highly hydrophilic in nature, and therefore tend to show low ion yields in both positive- and negative-ion modes. The labile nature and complicated branched structures involving various linkage isomers make structural characterization difficult. This review focuses on MALDI-MS-based approaches for enhancing analytical performance in N-glycosylation research. In particular, the following three topics are emphasized: (1) Labeling for enhancing the ion yields of glycans and glycopeptides, (2) Negative-ion fragmentation for less ambiguous elucidation of the branched structure of N-glycans, (3) Derivatization for the stabilization and linkage isomer discrimination of sialic acid residues. PMID:28794918

Vanadium fine-structure K-shell electron impact ionization cross sections for fast-electron diagnostic in laser–solid experiments

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

Palmeri, P., E-mail: patrick.palmeri@umons.ac.be; Quinet, P., E-mail: pascal.quinet@umons.ac.be; IPNAS, Université de Liège, B-4000 Liège

2015-09-15

The K-shell electron impact ionization (EII) cross section, along with the K-shell fluorescence yield, is one of the key atomic parameters for fast-electron diagnostic in laser–solid experiments through the K-shell emission cross section. In addition, in a campaign dedicated to the modeling of the K lines of astrophysical interest (Palmeri et al. (2012)), the K-shell fluorescence yields for the K-vacancy fine-structure atomic levels of all the vanadium isonuclear ions have been calculated. In this study, the K-shell EII cross sections connecting the ground and the metastable levels of the parent vanadium ions to the daughter ions K-vacancy levels considered in Palmerimore » et al. (2012) have been determined. The relativistic distorted-wave (DW) approximation implemented in the FAC atomic code has been used for the incident electron kinetic energies up to 20 times the K-shell threshold energies. Moreover, the resulting DW cross sections have been extrapolated at higher energies using the asymptotic behavior of the modified relativistic binary encounter Bethe model (MRBEB) of Guerra et al. (2012) with the density-effect correction proposed by Davies et al. (2013)« less

Discrimination of Aspergillus isolates at the species and strain level by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry fingerprinting.

PubMed

Hettick, Justin M; Green, Brett J; Buskirk, Amanda D; Kashon, Michael L; Slaven, James E; Janotka, Erika; Blachere, Francoise M; Schmechel, Detlef; Beezhold, Donald H

2008-09-15

Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) was used to generate highly reproducible mass spectral fingerprints for 12 species of fungi of the genus Aspergillus and 5 different strains of Aspergillus flavus. Prior to MALDI-TOF MS analysis, the fungi were subjected to three 1-min bead beating cycles in an acetonitrile/trifluoroacetic acid solvent. The mass spectra contain abundant peaks in the range of 5 to 20kDa and may be used to discriminate between species unambiguously. A discriminant analysis using all peaks from the MALDI-TOF MS data yielded error rates for classification of 0 and 18.75% for resubstitution and cross-validation methods, respectively. If a subset of 28 significant peaks is chosen, resubstitution and cross-validation error rates are 0%. Discriminant analysis of the MALDI-TOF MS data for 5 strains of A. flavus using all peaks yielded error rates for classification of 0 and 5% for resubstitution and cross-validation methods, respectively. These data indicate that MALDI-TOF MS data may be used for unambiguous identification of members of the genus Aspergillus at both the species and strain levels.

Advanced PIC-MCC simulation for the investigation of step-ionization effect in intermediate-pressure capacitively coupled plasmas

NASA Astrophysics Data System (ADS)

Kim, Jin Seok; Hur, Min Young; Kim, Chang Ho; Kim, Ho Jun; Lee, Hae June

2018-03-01

A two-dimensional parallelized particle-in-cell simulation has been developed to simulate a capacitively coupled plasma reactor. The parallelization using graphics processing units is applied to resolve the heavy computational load. It is found that the step-ionization plays an important role in the intermediate gas pressure of a few Torr. Without the step-ionization, the average electron density decreases while the effective electron temperature increases with the increase of gas pressure at a fixed power. With the step-ionization, however, the average electron density increases while the effective electron temperature decreases with the increase of gas pressure. The cases with the step-ionization agree well with the tendency of experimental measurement. The electron energy distribution functions show that the population of electrons having intermediate energy from 4.2 to 12 eV is relaxed by the step-ionization. Also, it was observed that the power consumption by the electrons is increasing with the increase of gas pressure by the step-ionization process, while the power consumption by the ions decreases with the increase of gas pressure.

Unified solution of the Boltzmann equation for electron and ion velocity distribution functions and transport coefficients in weakly ionized plasmas

NASA Astrophysics Data System (ADS)

Konovalov, Dmitry A.; Cocks, Daniel G.; White, Ronald D.

2017-10-01

The velocity distribution function and transport coefficients for charged particles in weakly ionized plasmas are calculated via a multi-term solution of Boltzmann's equation and benchmarked using a Monte-Carlo simulation. A unified framework for the solution of the original full Boltzmann's equation is presented which is valid for ions and electrons, avoiding any recourse to approximate forms of the collision operator in various limiting mass ratio cases. This direct method using Lebedev quadratures over the velocity and scattering angles avoids the need to represent the ion mass dependence in the collision operator through an expansion in terms of the charged particle to neutral mass ratio. For the two-temperature Burnett function method considered in this study, this amounts to avoiding the need for the complex Talmi-transformation methods and associated mass-ratio expansions. More generally, we highlight the deficiencies in the two-temperature Burnett function method for heavy ions at high electric fields to calculate the ion velocity distribution function, even though the transport coefficients have converged. Contribution to the Topical Issue "Physics of Ionized Gases (SPIG 2016)", edited by Goran Poparic, Bratislav Obradovic, Dragana Maric and Aleksandar Milosavljevic.

Ionization of biomolecular targets by ion impact: input data for radiobiological applications

NASA Astrophysics Data System (ADS)

de Vera, Pablo; Abril, Isabel; Garcia-Molina, Rafael; Solov'yov, Andrey V.

2013-06-01

In this work we review and further develop a semiempirical model recently proposed for the ion impact ionization of complex biological media. The model is based on the dielectric formalism, and makes use of a semiempirical parametrization of the optical energy-loss function of bioorganic compounds, allowing the calculation of single and total ionization cross sections and related quantities for condensed biological targets, such as liquid water, DNA and its components, proteins, lipids, carbohydrates or cell constituents. The model shows a very good agreement with experimental data for water, adenine and uracil, and allows the comparison of the ionization efficiency of different biological targets, and also the average kinetic energy of the ejected secondary electrons.

Multi-photon ionization of atoms in intense short-wavelength radiation fields

NASA Astrophysics Data System (ADS)

Meyer, Michael

2015-05-01

The unprecedented characteristics of XUV and X-ray Free Electron Lasers (FELs) have stimulated numerous investigations focusing on the detailed understanding of fundamental photon-matter interactions in atoms and molecules. In particular, the high intensities (up to 106 W/cm2) giving rise to non-linear phenomena in the short wavelength regime. The basic phenomenology involves the production of highly charged ions via electron emission to which both sequential and direct multi-photon absorption processes contribute. The detailed investigation of the role and relative weight of these processes under different conditions (wavelength, pulse duration, intensity) is the key element for a comprehensive understanding of the ionization dynamics. Here the results of recent investigations are presented, performed at the FELs in Hamburg (FLASH) and Trieste (FERMI) on atomic systems with electronic structures of increasing complexity (Ar, Ne and Xe). Mainly, electron spectroscopy is used to obtain quantitative information about the relevance of various multi-photon ionization processes. For the case of Ar, a variety of processes including above threshold ionization (ATI) from 3p and 3s valence shells, direct 2p two-photon ionization and resonant 2p-4p two-photon excitations were observed and their role was quantitatively determined comparing the experimental ionization yields to ab-initio calculations of the cross sections for the multi-photon processes. Using Ar as a benchmark to prove the reliability of the combined experimental and theoretical approach, the more complex and intriguing case of Xe was studied. Especially, the analysis of the two-photon ATI from the Xe 4d shell reveals new insight into the character of the 4d giant resonance, which was unresolved in the linear one-photon regime. Finally, the influence of intense XUV radiation to the relaxation dynamics of the Ne 2s-3p resonance was investigated by angle-resolved electron spectroscopy, especially be observing the intensity dependent variation of the angular distribution patterns for the sequential ionization process.

Relationships between structure, ionization profile and sensitivity of exogenous anabolic steroids under electrospray ionization and analysis in human urine using liquid chromatography-tandem mass spectrometry.

PubMed

Cha, Eunju; Kim, Sohee; Kim, Hee Won; Lee, Kang Mi; Kim, Ho Jun; Kwon, Oh-Seung; Lee, Jaeick

2016-04-01

The relationships between the ionization profile, sensitivity, and structures of 64 exogenous anabolic steroids (groups I-IV) was investigated under electrospray ionization (ESI) conditions. The target analytes were ionized as [M + H](+) or [M + H-nH2 O](+) in the positive mode, and these ions were used as precursor ions for selected reaction monitoring analysis. The collision energy and Q3 ions were optimized based on the sensitivity and selectivity. The limits of detection (LODs) were 0.05-20 ng/mL for the 64 steroids. The LODs for 38 compounds, 14 compounds and 12 compounds were in the range of 0.05-1, 2-5 and 10-20 ng/mL, respectively. Steroids including the conjugated keto-functional group at C3 showed good proton affinity and stability, and generated the [M + H](+) ion as the most abundant precursor ion. In addition, the LODs of steroids using the [M + H](+) ion as the precursor ion were mostly distributed at low concentrations. In contrast, steroids containing conjugated/unconjugated hydroxyl functional groups at C3 generated [M + H - H2 O](+) or [M + H - 2H2 O](+) ions, and these steroids showed relatively high LODs owing to poor stability and multiple ion formation. An LC-MS/MS method based on the present ionization profile was developed and validated for the determination of 78 steroids (groups I-V) in human urine. Copyright © 2015 John Wiley & Sons, Ltd.

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

Watanabe, N.; Takahashi, M.; Institute of Multidisciplinary Research for Advanced Materials, Tohoku University, Sendai 980-8577

The double processes of He in electron-impact ionization, single ionization with simultaneous excitation and double ionization, have been studied at large momentum transfer using an energy- and momentum-dispersive binary (e,2e) spectrometer. The experiment has been performed at an impact energy of 2080 eV in the symmetric noncoplanar geometry. In this way we have achieved a large momentum transfer of 9 a.u., a value that has never been realized so far for the study on double ionization. The measured (e,2e) and (e,3-1e) cross sections for transitions to the n=2 excited state of He{sup +} and to doubly ionized He{sup 2+} aremore » presented as normalized intensities relative to that to the n=1 ground state of He{sup +}. The results are compared with first-order plane-wave impulse approximation (PWIA) calculations using various He ground-state wave functions. It is shown that shapes of the momentum-dependent (e,2e) and (e,3-1e) cross sections are well reproduced by the PWIA calculations only when highly correlated wave functions are employed. However, noticeable discrepancies between experiment and theory remain in magnitude for both the double processes, suggesting the importance of higher-order effects under the experimental conditions examined as well as of acquiring more complete knowledge of electron correlation in the target.« less

Renormalization group method based on the ionization energy theory

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

Arulsamy, Andrew Das, E-mail: sadwerdna@gmail.com; School of Physics, University of Sydney, Sydney, New South Wales 2006

2011-03-15

Proofs are developed to explicitly show that the ionization energy theory is a renormalized theory, which mathematically exactly satisfies the renormalization group formalisms developed by Gell-Mann-Low, Shankar and Zinn-Justin. However, the cutoff parameter for the ionization energy theory relies on the energy-level spacing, instead of lattice point spacing in k-space. Subsequently, we apply the earlier proofs to prove that the mathematical structure of the ionization-energy dressed electron-electron screened Coulomb potential is exactly the same as the ionization-energy dressed electron-phonon interaction potential. The latter proof is proven by means of the second-order time-independent perturbation theory with the heavier effective mass condition,more » as required by the electron-electron screened Coulomb potential. The outcome of this proof is that we can derive the heat capacity and the Debye frequency as a function of ionization energy, which can be applied in strongly correlated matter and nanostructures.« less

Electronic and ionization spectra of 1,1-diamino-2,2-dinitroethylene, FOX-7.

PubMed

Borges, Itamar

2014-03-01

Singlet, triplet and ionized states of the energetic molecule 1,1-diamino-2,2-dinitroethylene, known as FOX-7 or DADNE, were investigated using the symmetry-adapted-cluster configuration interaction (SAC-CI) ab initio wave function. The 20 computed singlet transitions, with 2 exceptions, were bright. The most intense singlet transitions were of the n₀→π type-typical of molecules having nitro groups. Fast intersystem crossing (ISC) from the 1¹A, 2¹A and 8¹A bright singlet transitions is possible. Other feasible ISC processes are discussed. The computed singlet and ionization spectra have similar features when compared to nitramide and N,N-dimethylnitramine molecules, which have only a nitro group. The ionization energies of the first 20 states have differences in comparison with Koopmans' energy values that can reach 3 eV. Moreover, the character of the first ionized states, dominated by single ionizations, is not the same when compared with the character resulting from application of Koopmans' theorem.

Collision cross sections of N2 by H+ impact at keV energies within time-dependent density-functional theory

NASA Astrophysics Data System (ADS)

Yu, W.; Gao, C.-Z.; Zhang, Y.; Zhang, F. S.; Hutton, R.; Zou, Y.; Wei, B.

2018-03-01

We calculate electron capture and ionization cross sections of N2 impacted by the H+ projectile at keV energies. To this end, we employ the time-dependent density-functional theory coupled nonadiabatically to molecular dynamics. To avoid the explicit treatment of the complex density matrix in the calculation of cross sections, we propose an approximate method based on the assumption of constant ionization rate over the period of the projectile passing the absorbing boundary. Our results agree reasonably well with experimental data and semi-empirical results within the measurement uncertainties in the considered energy range. The discrepancies are mainly attributed to the inadequate description of exchange-correlation functional and the crude approximation for constant ionization rate. Although the present approach does not predict the experiments quantitatively for collision energies below 10 keV, it is still helpful to calculate total cross sections of ion-molecule collisions within a certain energy range.

Site-directed mutagenesis of the conserved Asp-443 and Asp-498 carboxy-terminal residues of HIV-1 reverse transcriptase.

PubMed Central

Mizrahi, V; Usdin, M T; Harington, A; Dudding, L R

1990-01-01

Substitution of the conserved Asp-443 residue of HIV-1 reverse transcriptase by asparagine specifically suppressed the ribonuclease H activity of the enzyme without affecting the reverse transcriptase activity, suggesting involvement of this ionizable residue at the ribonuclease H active site. An analogous asparagine substitution of the Asp-498 residue yielded an unstable enzyme that was difficult to enzymatically characterize. However, the instability caused by the Asn-498 mutation was relieved by the introduction of a second distal Asn-443 substitution, yielding an enzyme with wild type reverse transcriptase activity, but lacking ribonuclease H activity. Images PMID:1699202

Ionization compression impact on dense gas distribution and star formation. Probability density functions around H II regions as seen by Herschel

NASA Astrophysics Data System (ADS)

Tremblin, P.; Schneider, N.; Minier, V.; Didelon, P.; Hill, T.; Anderson, L. D.; Motte, F.; Zavagno, A.; André, Ph.; Arzoumanian, D.; Audit, E.; Benedettini, M.; Bontemps, S.; Csengeri, T.; Di Francesco, J.; Giannini, T.; Hennemann, M.; Nguyen Luong, Q.; Marston, A. P.; Peretto, N.; Rivera-Ingraham, A.; Russeil, D.; Rygl, K. L. J.; Spinoglio, L.; White, G. J.

2014-04-01

Aims: Ionization feedback should impact the probability distribution function (PDF) of the column density of cold dust around the ionized gas. We aim to quantify this effect and discuss its potential link to the core and initial mass function (CMF/IMF). Methods: We used Herschel column density maps of several regions observed within the HOBYS key program in a systematic way: M 16, the Rosette and Vela C molecular clouds, and the RCW 120 H ii region. We computed the PDFs in concentric disks around the main ionizing sources, determined their properties, and discuss the effect of ionization pressure on the distribution of the column density. Results: We fitted the column density PDFs of all clouds with two lognormal distributions, since they present a "double-peak" or an enlarged shape in the PDF. Our interpretation is that the lowest part of the column density distribution describes the turbulent molecular gas, while the second peak corresponds to a compression zone induced by the expansion of the ionized gas into the turbulent molecular cloud. Such a double peak is not visible for all clouds associated with ionization fronts, but it depends on the relative importance of ionization pressure and turbulent ram pressure. A power-law tail is present for higher column densities, which are generally ascribed to the effect of gravity. The condensations at the edge of the ionized gas have a steep compressed radial profile, sometimes recognizable in the flattening of the power-law tail. This could lead to an unambiguous criterion that is able to disentangle triggered star formation from pre-existing star formation. Conclusions: In the context of the gravo-turbulent scenario for the origin of the CMF/IMF, the double-peaked or enlarged shape of the PDF may affect the formation of objects at both the low-mass and the high-mass ends of the CMF/IMF. In particular, a broader PDF is required by the gravo-turbulent scenario to fit the IMF properly with a reasonable initial Mach number for the molecular cloud. Since other physical processes (e.g., the equation of state and the variations among the core properties) have already been said to broaden the PDF, the relative importance of the different effects remains an open question. Herschel is an ESA space observatory with science instruments provided by European-led Principal Investigator consortia and with important participation from NASA.

Unraveling the Helix Nebula: Its Structure and Knots

NASA Astrophysics Data System (ADS)

O'Dell, C. R.; McCullough, Peter R.; Meixner, Margaret

2004-11-01

Through Hubble Space Telescope (HST) imaging of the inner part of the main ring of the Helix Nebula, together with CTIO 4 m images of the fainter outer parts, we have a view of unprecedented quality of the nearest bright planetary nebula. These images have allowed us to determine that the main ring of the nebula is composed of an inner disk of about 499" diameter (0.52 pc) surrounded by an outer ring (in reality a torus) of 742" diameter (0.77 pc) whose plane is highly inclined to the plane of the disk. This outer ring is surrounded by an outermost ring of 1500" (1.76 pc) diameter, which is flattened on the side colliding with the ambient interstellar medium. The inner disk has an extended distribution of low-density gas along its rotational axis of symmetry, and the disk is optically thick to ionizing radiation, as is the outer ring. Published radial velocities of the knots provide support for the two-component structure of the main ring of the nebula and for the idea that the knots found there are expanding along with the nebular material from which they recently originated. These velocities indicate a spatial expansion velocity of the inner disk of 40 and 32 km s-1 for the outer ring, which yields expansion ages of 6560 and 12,100 yr, respectively. The outermost ring may be partially ionized through scattered recombination continuum from the inner parts of the nebula, but shocks certainly are occurring in it. This outermost ring probably represents a third period of mass loss by the central star. There is one compact, outer object that is unexplained, showing shock structures indicating a different orientation of the gas flow from that of the nebula. There is a change in the morphology of the knots as a function of the distance from the local ionization front. This supports a scenario in which the knots are formed in or near the ionization front and are then sculpted by the stellar radiation from the central star as the ionization front advances beyond them. Based in part on observations with the NASA/ESA Hubble Space Telescope, obtained at the Space Telescope Science Institute, which is operated by the Association of Universities for Research in Astronomy, Inc., under NASA contract NAS5-26555. Based in part on observations obtained at the Cerro Tololo Inter-American Observatory, which is operated by the Association of Universities for Research in Astronomy, Inc., under a Cooperative Agreement with the National Science Foundation.

Effects of ionizing radiation on charge-coupled imagers

NASA Technical Reports Server (NTRS)

Killiany, J. M.; Baker, W. D.; Saks, N. S.; Barbe, D. F.

1975-01-01

The effects of ionizing radiation on three different charge coupled imagers have been investigated. Device performance was evaluated as a function of total gamma ray dose. The principal failure mechanisms have been identified for each particular device structure. The clock and bias voltages required for high total dose operation of the devices are presented.

Methemoglobinemia hemotoxicity of some antimalarial 8-aminoquinoline analogues and their hydroxylated derivatives: density functional theory computation of ionization potentials

USDA-ARS?s Scientific Manuscript database

The administration of primaquine (PQ), an essential drug for treatment and radical cure of malaria, can lead to methemoglobin formation and life-threatening hemolysis for glucose-6-phosphate dehydrogenase deficient patients. The ionization potential (IP, a quantitative measure of the ability to lose...

A high pressure hollow cathode ionization source for in-situ detection of organic molecules on Mars

NASA Technical Reports Server (NTRS)

Beegle, Luther W.; Kanik, Isik

2001-01-01

We have designed, constructed and characterized a new high-pressure (1-5 Torr) hollow cathode discharge source (HCDSj that can be utilized as an ionizer in a wide variety of mass analyzers. It is able to function under ambient Martian atmospheric conditions without modification.

Past Exposure to Densely Ionizing Radiation Leaves a Unique Permanent Signature in the Genome

PubMed Central

Hande, M. Prakash; Azizova, Tamara V.; Geard, Charles R.; Burak, Ludmilla E.; Mitchell, Catherine R.; Khokhryakov, Valentin F.; Vasilenko, Evgeny K.; Brenner, David J.

2003-01-01

Speculation has long surrounded the question of whether past exposure to ionizing radiation leaves a unique permanent signature in the genome. Intrachromosomal rearrangements or deletions are produced much more efficiently by densely ionizing radiation than by chemical mutagens, x-rays, or endogenous aging processes. Until recently, such stable intrachromosomal aberrations have been very hard to detect, but a new chromosome band painting technique has made their detection practical. We report the detection and quantification of stable intrachromosomal aberrations in lymphocytes of healthy former nuclear-weapons workers who were exposed to plutonium many years ago. Even many years after occupational exposure, more than half the blood cells of the healthy plutonium workers contain large (>6 Mb) intrachromosomal rearrangements. The yield of these aberrations was highly correlated with plutonium dose to the bone marrow. The control groups contained very few such intrachromosomal aberrations. Quantification of this large-scale chromosomal damage in human populations exposed many years earlier will lead to new insights into the mechanisms and risks of cytogenetic damage. PMID:12679897

Pretreatment of grass waste using combined ionizing radiation-acid treatment for enhancing fermentative hydrogen production.

PubMed

Yang, Guang; Wang, Jianlong

2018-05-01

In this study, the combined ionizing radiation-acid pretreatment process was firstly applied to enhance hydrogen fermentation of grass waste. Results showed that the combined pretreatment synergistically enhanced hydrogen fermentation of grass waste. The SCOD and soluble polysaccharide contents of grass waste increased by 1.6 and 2.91 times after the combined pretreatment, respectively. SEM observation and crystallinity test showed the combined pretreatment effectively disrupted the grass structure. Owing to the more favorable substrate conditions, the hydrogen yield achieved 68 mL/g-dry grass added after the combined pretreatment, which was 161.5%, 112.5% and 28.3% higher than those from raw, ionizing radiation pretreated and acid pretreated grass waste, respectively. The VS removal also increased from 13.9% to 25.6% by the combined pretreatment. Microbial community analysis showed that the abundance of dominant hydrogen producing genus Clostridium sensu stricto 1 increased from 37.9% to 69.4% after the combined pretreatment, which contributed to more efficient hydrogen fermentation. Copyright © 2018 Elsevier Ltd. All rights reserved.

Multiple outer-shell ionization effect in inner-shell x-ray production by light ions

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

Lapicki, G.; Mehta, R.; Duggan, J.L.

1986-11-01

L-shell x-ray production cross sections by 0.25--2.5-MeV /sub 2//sup 4/He/sup +/ ions in /sub 28/Ni, /sub 29/Cu, /sub 32/Ge, /sub 33/As, /sub 37/Rb, /sub 38/Sr, /sub 39/Y, /sub 40/Zr, and /sub 46/Pd are reported. The data are compared to the first Born approximation and the ECPSSR theory that accounts for the projectile energy loss (E) and Coulomb deflection (C) as well as the perturbed-stationary-state (PSS) and relativistic (R) effects in the treatment of the target L-shell electron. Surprisingly, the first Born approximation appears to converge to the data while the ECPSSR predictions underestimate them in the low-velocity limit. This ismore » explained as the result of improper use of single-hole fluorescence yields. A heuristic formula is proposed to account for multiple ionizations in terms of a classical probability for these phenomena and, after it is applied, the ECPSSR theory of L-shell ionization is found to be in good agreement with the data.« less

Fragmentation of neutral amino acids and small peptides by intense, femtosecond laser pulses.

PubMed

Duffy, Martin J; Kelly, Orla; Calvert, Christopher R; King, Raymond B; Belshaw, Louise; Kelly, Thomas J; Costello, John T; Timson, David J; Bryan, William A; Kierspel, Thomas; Turcu, I C Edmond; Cacho, Cephise M; Springate, Emma; Williams, Ian D; Greenwood, Jason B

2013-09-01

High power femtosecond laser pulses have unique properties that could lead to their application as ionization or activation sources in mass spectrometry. By concentrating many photons into pulse lengths approaching the timescales associated with atomic motion, very strong electric field strengths are generated, which can efficiently ionize and fragment molecules without the need for resonant absorption. However, the complex interaction between these pulses and biomolecular species is not well understood. To address this issue, we have studied the interaction of intense, femtosecond pulses with a number of amino acids and small peptides. Unlike previous studies, we have used neutral forms of these molecular targets, which allowed us to investigate dissociation of radical cations without the spectra being complicated by the action of mobile protons. We found fragmentation was dominated by fast, radical-initiated dissociation close to the charge site generated by the initial ionization or from subsequent ultrafast migration of this charge. Fragments with lower yields, which are useful for structural determinations, were also observed and attributed to radical migration caused by hydrogen atom transfer within the molecule.

Method for selective detection of explosives in mass spectrometer or ion mobility spectrometer at parts-per-quadrillion level

DOEpatents

Ewing, Robert G.; Atkinson, David A.; Clowers, Brian H.

2015-09-01

A method for selective detection of volatile and non-volatile explosives in a mass spectrometer or ion mobility spectrometer at a parts-per-quadrillion level without preconcentration is disclosed. The method comprises the steps of ionizing a carrier gas with an ionization source to form reactant ions or reactant adduct ions comprising nitrate ions (NO.sub.3.sup.-); selectively reacting the reactant ions or reactant adduct ions with at least one volatile or non-volatile explosive analyte at a carrier gas pressure of at least about 100 Ton in a reaction region disposed between the ionization source and an ion detector, the reaction region having a length which provides a residence time (tr) for reactant ions therein of at least about 0.10 seconds, wherein the selective reaction yields product ions comprising reactant ions or reactant adduct ions that are selectively bound to the at least one explosive analyte when present therein; and detecting product ions with the ion detector to determine presence or absence of the at least one explosive analyte.

Theoretical model of the plasma edge. II. Transport along the open field lines of a magnetic island belt associated with the ionization instability

NASA Astrophysics Data System (ADS)

Rogister, A. L. M.; Hasselberg, G.

1993-12-01

For pt.I, see ibid, p.1799-1816 (1993). To the ionization instability described in Part I correspond odd phi, even br eigenfunctions leading, as for the tearing mode, to a magnetic island belt centred about the rational magnetic surface q = m < qa (q is the safety factor; m is the mode number). Plasma dumping on the target plates, along the island magnetic field lines, releases the neutrals, the ionization of which drives the instability. This self-consistent model of the plasma edge yields the electron temperature on the last closed equilibrium magnetic surface and the particle confinement time, which are compared with the values measured in TEXTOR and other tokamaks; interestingly, the value obtained for τp is very reminiscent of the heuristic energy confinement time expression proposed by Kaye and Goldston(1985). Theory also predicts an equilibrium bifurcation at high power, corresponding to a reduction, and then a collapse, of the island width. The hypothesis that the (L mode) island belt be hooked up to the machine's structure is briefly discussed

Determination of drug lipophilicity by phosphatidylcholine-modified microemulsion high-performance liquid chromatography.

PubMed

Xuan, Xueyi; Xu, Liyuan; Li, Liangxing; Gao, Chongkai; Li, Ning

2015-07-25

A new biomembrane-mimetic liquid chromatographic method using a C8 stationary phase and phosphatidylcholine-modified (PC-modified) microemulsion mobile phase was used to estimate unionized and ionized drugs lipophilicity expressed as an n-octanol/water partition coefficient (logP and logD). The introduction of PC into sodium dodecyl sulfate (SDS) microemulsion yielded a good correlation between logk and logD (R(2)=0.8). The optimal composition of the PC-modified microemulsion liquid chromatography (PC-modified MELC) mobile phase was 0.2% PC-3.0% SDS-6.0% n-butanol-0.8% ethyl acetate-90.0% water (pH 7.0) for neutral and ionized molecules. The interactions between the analytes and system described by this chromatographic method is more similar to biological membrane than the n-octanol/water partition system. The result in this paper suggests that PC-modified MELC can serve as a possible alternative to the shake-flask method for high-throughput unionized and ionized drugs lipophilicity determination and simulation of biological processes. Copyright © 2015 Elsevier B.V. All rights reserved.

Dissociation of dicyclohexyl phthalate molecule induced by low-energy electron impact

NASA Astrophysics Data System (ADS)

Lacko, Michal; Papp, Peter; Matejčík, Štefan

2018-06-01

Experimental investigation of electron ionization (EI) of and electron attachment (EA) onto dicyclohexyl phthalate (DCHP) was carried out using a crossed electron and molecular beam technique. Formation of positive and negative ions by EI and EA with the corresponding dissociation processes was studied and discussed. Due to a low ion yield of the parent positive ion, we were not able to estimate the ionization energy of DCHP. However, we estimated the appearance energies for the protonated phthalate anhydride (m/z 149) to be 10.5 eV and other significant ionic fragments of m/z 249 [DCHP—(R—2H)]+, m/z 167 [DCHP—(2R—3H)]+, and m/z 83 [C6H11]+. The reaction mechanisms of the dissociative ionization process were discussed. In the case of negative ions, we estimated the relative cross sections for a transient negative ion (TNI) and for several detected ions. At low electron energies (close to 0 eV), the TNI of DCHP molecules was the dominant ion, with products of dissociative EA dominating in broad resonances at 7.5 and 8.5 eV.

Enhanced MALDI-TOF MS Analysis of Phosphopeptides Using an Optimized DHAP/DAHC Matrix

PubMed Central

Hou, Junjie; Xie, Zhensheng; Xue, Peng; Cui, Ziyou; Chen, Xiulan; Li, Jing; Cai, Tanxi; Wu, Peng; Yang, Fuquan

2010-01-01

Selecting an appropriate matrix solution is one of the most effective means of increasing the ionization efficiency of phosphopeptides in matrix-assisted laser-desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS). In this study, we systematically assessed matrix combinations of 2, 6-dihydroxyacetophenone (DHAP) and diammonium hydrogen citrate (DAHC), and demonstrated that the low ratio DHAP/DAHC matrix was more effective in enhancing the ionization of phosphopeptides. Low femtomole level of phosphopeptides from the tryptic digests of α-casein and β-casein was readily detected by MALDI-TOF-MS in both positive and negative ion mode without desalination or phosphopeptide enrichment. Compared with the DHB/PA matrix, the optimized DHAP/DAHC matrix yielded superior sample homogeneity and higher phosphopeptide measurement sensitivity, particularly when multiple phosphorylated peptides were assessed. Finally, the DHAP/DAHC matrix was applied to identify phosphorylation sites from α-casein and β-casein and to characterize two phosphorylation sites from the human histone H1 treated with Cyclin-Dependent Kinase-1 (CDK1) by MALDI-TOF/TOF MS. PMID:20339515

Screening of exciplex formation by distant electron transfer.

PubMed

Fedorenko, S G; Khokhlova, S S; Burshtein, A I

2012-01-12

The excitation quenching by reversible exciplex formation, combined with irreversible but distant electron transfer, is considered by means of the integral encounter theory (IET). Assuming that the quenchers are in great excess, the set of IET equations for the excitations, free ions, and exciplexes is derived. Solving these equations gives the Laplace images of all these populations, and these are used to specify the quantum yields of the corresponding reaction products. It appears that diffusion facilitates the exciplex production and the electron transfer. On the other hand the stronger the electron transfer is, the weaker is the exciplex production. At slow diffusion the distant quenching of excitations by ionization prevents their reaching the contact where they can turn into exciplexes. This is a screening effect that is most pronounced when the ionization rate is large.

Structural characterization of phospholipids by matrix-assisted laser desorption/ionization Fourier transform ion cyclotron resonance mass spectrometry.

PubMed

Marto, J A; White, F M; Seldomridge, S; Marshall, A G

1995-11-01

Matrix-assisted laser desorption/ionization (MALDI) Fourier transform ion cyclotron resonance mass spectrometry provides for structural analysis of the principal biological phospholipids: glycerophosphatidylcholine, -ethanolamine, -serine, and -inositol. Both positive and negative molecular or quasimolecular ions are generated in high abundance. Isolated molecular ions may be collisionally activated in the source side of a dual trap mass analyzer, yielding fragments serving to identify the polar head group (positive ion mode) and fatty acid side chains (negative ion mode). Azimuthal quadrupolar excitation following collisionally activated dissociation refocuses productions close to the solenoid axis; subsequent transfer of product ions to the analyzer ion trap allows for high-resolution mass analysis. Cyro-cooling of the sample probe with liquid nitrogen greatly reduces matrix adduction encountered in the negative ion mode.

CMOS sensor as charged particles and ionizing radiation detector

NASA Astrophysics Data System (ADS)

Cruz-Zaragoza, E.; Piña López, I.

2015-01-01

This paper reports results of CMOS sensor suitable for use as charged particles and ionizing radiation detector. The CMOS sensor with 640 × 480 pixels area has been integrated into an electronic circuit for detection of ionizing radiation and it was exposed to alpha particle (Am-241, Unat), beta (Sr-90), and gamma photons (Cs-137). Results show after long period of time (168 h) irradiation the sensor had not loss of functionality and also the energy of the charge particles and photons were very well obtained.

A Radical-Mediated Pathway for the Formation of [M + H](+) in Dielectric Barrier Discharge Ionization.

PubMed

Wolf, Jan-Christoph; Gyr, Luzia; Mirabelli, Mario F; Schaer, Martin; Siegenthaler, Peter; Zenobi, Renato

2016-09-01

Active capillary plasma ionization is a highly efficient ambient ionization method. Its general principle of ion formation is closely related to atmospheric pressure chemical ionization (APCI). The method is based on dielectric barrier discharge ionization (DBDI), and can be constructed in the form of a direct flow-through interface to a mass spectrometer. Protonated species ([M + H](+)) are predominantly formed, although in some cases radical cations are also observed. We investigated the underlying ionization mechanisms and reaction pathways for the formation of protonated analyte ([M + H](+)). We found that ionization occurs in the presence and in the absence of water vapor. Therefore, the mechanism cannot exclusively rely on hydronium clusters, as generally accepted for APCI. Based on isotope labeling experiments, protons were shown to originate from various solvents (other than water) and, to a minor extent, from gaseous impurities and/or self-protonation. By using CO2 instead of air or N2 as plasma gas, additional species like [M + OH](+) and [M - H](+) were observed. These gas-phase reaction products of CO2 with the analyte (tertiary amines) indicate the presence of a radical-mediated ionization pathway, which proceeds by direct reaction of the ionized plasma gas with the analyte. The proposed reaction pathway is supported with density functional theory (DFT) calculations. These findings add a new ionization pathway leading to the protonated species to those currently known for APCI. Graphical Abstract ᅟ.

Taurine Protects Mouse Spermatocytes from Ionizing Radiation-Induced Damage Through Activation of Nrf2/HO-1 Signaling.

PubMed

Yang, Wenjun; Huang, Jinfeng; Xiao, Bang; Liu, Yan; Zhu, Yiqing; Wang, Fang; Sun, Shuhan

2017-01-01

The increasing prevalence of ionizing radiation exposure has inevitably raised public concern over the potential detrimental effects of ionizing radiation on male reproductive system function. The detection of drug candidates to prevent reproductive system from damage caused by ionizing radiation is urgent. We aimed to investigate the protective role of taurine on the injury of mouse spermatocyte-derived cells (GC-2) subjected to ionizing radiation. mouse spermatocytes (GC-2 cells) were exposed to ionizing radiation with or without treatment of Taurine. The effect of ionizing radiation and Taurine treatment on GC-2 cells were evaluated by cell viability assay (CCK8), cell cycle and apoptosis. The relative protein abundance change was determined by Western blotting. The siRNA was used to explore whether Nrf2 signaling was involved in the cytoprotection of Taurine. Taurine significantly inhibited the decrease of cell viability, percentage of apoptotic cells and cell cycle arrest induced by ionizing radiation. Western blot analysis showed that taurine significantly limited the ionizing radiation-induced down-regulation of CyclinB1 and CDK1, and suppressed activation of Fas/FasL system pathway. In addition, taurine treatment significantly increased the expression of Nrf2 and HO-1 in GC-2 cells exposed to ionizing radiation, two components in antioxidant pathway. The above cytoprotection of Taurine was blocked by siNrf2. Our results demonstrate that taurine has the potential to effectively protect GC-2 cells from ionizing radiation- triggered damage via upregulation of Nrf2/HO-1 signaling. © 2017 The Author(s). Published by S. Karger AG, Basel.

Flash ionization signature in coherent cyclotron emission from brown dwarfs

NASA Astrophysics Data System (ADS)

Vorgul, I.; Helling, Ch.

2016-05-01

Brown dwarfs (BDs) form mineral clouds in their atmospheres, where charged particles can produce large-scale discharges in the form of lightning resulting in substantial sudden increase of local ionization. BDs are observed to emit cyclotron radio emission. We show that signatures of strong transient atmospheric ionization events (flash ionization) can be imprinted on a pre-existing radiation. Detection of such flash ionization events will open investigations into the ionization state and atmospheric dynamics. Such events can also result from explosion shock waves, material outbursts or (volcanic) eruptions. We present an analytical model that describes the modulation of a pre-existing electromagnetic radiation by a time-dependent (flash) conductivity that is characteristic for flash ionization events like lightning. Our conductivity model reproduces the conductivity function derived from observations of terrestrial gamma-ray flashes, and is applicable to astrophysical objects with strong temporal variations in the local ionization, as in planetary atmospheres and protoplanetary discs. We show that the field responds with a characteristic flash-shaped pulse to a conductivity flash of intermediate intensity. More powerful ionization events result in smaller variations of the initial radiation, or in its damping. We show that the characteristic damping of the response field for high-power initial radiation carries information about the ionization flash magnitude and duration. The duration of the pulse amplification or the damping is consistently shorter for larger conductivity variations and can be used to evaluate the intensity of the flash ionization. Our work suggests that cyclotron emission could be probe signals for electrification processes inside BD atmosphere.

Quantum Computational Calculations of the Ionization Energies of Acidic and Basic Amino Acids: Aspartate, Glutamate, Arginine, Lysine, and Histidine

NASA Astrophysics Data System (ADS)

de Guzman, C. P.; Andrianarijaona, M.; Lee, Y. S.; Andrianarijaona, V.

An extensive knowledge of the ionization energies of amino acids can provide vital information on protein sequencing, structure, and function. Acidic and basic amino acids are unique because they have three ionizable groups: the C-terminus, the N-terminus, and the side chain. The effects of multiple ionizable groups can be seen in how Aspartate's ionizable side chain heavily influences its preferred conformation (J Phys Chem A. 2011 April 7; 115(13): 2900-2912). Theoretical and experimental data on the ionization energies of many of these molecules is sparse. Considering each atom of the amino acid as a potential departing site for the electron gives insight on how the three ionizable groups affect the ionization process of the molecule and the dynamic coupling between the vibrational modes. In the following study, we optimized the structure of each acidic and basic amino acid then exported the three dimensional coordinates of the amino acids. We used ORCA to calculate single point energies for a region near the optimized coordinates and systematically went through the x, y, and z coordinates of each atom in the neutral and ionized forms of the amino acid. With the calculations, we were able to graph energy potential curves to better understand the quantum dynamic properties of the amino acids. The authors thank Pacific Union College Student Association for providing funds.

The interaction of an ionizing ligand with enzymes having a single ionizing group. Implications for the reaction of folate analogues with dihydrofolate reductase.

PubMed

Stone, S R; Morrison, J F

1983-06-29

Binding theory has been developed for the reaction of an ionizing enzyme with an ionizing ligand. Consideration has been given to the most general scheme in which all possible reactions and interconversions occur as well as to schemes in which certain interactions do not take place. Equations have been derived in terms of the variation of the apparent dissociation constant (Kiapp) as a function of pH. These equations indicate that plots of pKiapp against pH can be wave-, half-bell- or bell-shaped according to the reactions involved. A wave is obtained whenever there is formation of the enzyme-ligand complexes, ionized enzyme . ionized ligand and protonated enzyme . protonated ligand. The additional formation of singly protonated enzyme-ligand complexes does not affect the wave form of the plot, but can influence the shape of the overall curve. The formation of either ionized enzyme . ionized ligand or protonated enzyme . protonated ligand, with or without singly protonated enzyme-ligand species, gives rise to a half-bell-shaped plot. If only singly protonated enzyme-ligand complexes are formed the plots are bell-shaped, but it is not possible to deduce the ionic forms of the reactants that participate in complex formation. Depending on the reaction pathways, true values for the ionization and dissociation constants may or may not be determined.

Density functional theory calculations of continuum lowering in strongly coupled plasmas.

PubMed

Vinko, S M; Ciricosta, O; Wark, J S

2014-03-24

An accurate description of the ionization potential depression of ions in plasmas due to their interaction with the environment is a fundamental problem in plasma physics, playing a key role in determining the ionization balance, charge state distribution, opacity and plasma equation of state. Here we present a method to study the structure and position of the continuum of highly ionized dense plasmas using finite-temperature density functional theory in combination with excited-state projector augmented-wave potentials. The method is applied to aluminium plasmas created by intense X-ray irradiation, and shows excellent agreement with recently obtained experimental results. We find that the continuum lowering for ions in dense plasmas at intermediate temperatures is larger than predicted by standard plasma models and explain this effect through the electronic structure of the valence states in these strong-coupling conditions.

Implementation of ionizing radiation environment requirements for Space Station

NASA Technical Reports Server (NTRS)

Boeder, Paul A.; Watts, John W.

1993-01-01

Proper functioning of Space Station hardware requires that the effects of high-energy ionizing particles from the natural environment and (possibly) from man-made sources be considered during design. At the Space Station orbit of 28.5-deg inclination and 330-440 km altitude, geomagnetically trapped protons and electrons contribute almost all of the dose, while galactic cosmic rays and anomalous cosmic rays may produce Single Event Upsets (SEUs), latchups, and burnouts of microelectronic devices. Implementing ionizing radiation environment requirements for Space Station has been a two part process, including the development of a description of the environment for imposing requirements on the design and the development of a control process for assessing how well the design addresses the effects of the ionizing radiation environment. We will review both the design requirements and the control process for addressing ionizing radiation effects on Space Station.

THE EFFECT OF IONIZING RADIATIONS ON ONTOGENESIS IN BIRDS

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

Dinu, M.

1963-01-01

The effect of strong doses of ionizing radiations on the ontogenetic development of birds and formation of mutations was studied. The data obtained show that ionizing radiations have a different effect on the biological substratum, depending on their nature and relationship to physiological limits. Gamma radiations have a negative action on the biochemical process altering ths substratum and upsetting the entity of heredity. It was found that x rays produce a temporary stimulating effect on metabolic processes influencing the vitality, ontogenetic development, resistance, the appearance of sexual instinct, and the fertility. Ionizing radiations affect functioning of endocrinic glands and consequentlymore » the ratio of sexes in the offspring. From the results obtained it cand be stated that strong doses of ionizing radiations may be used to obtain variation of mutations, and that in general they are a factor in the evolution of the living organism. (OTS)« less

Acetonitrile Ion Suppression in Atmospheric Pressure Ionization Mass Spectrometry

NASA Astrophysics Data System (ADS)

Colizza, Kevin; Mahoney, Keira E.; Yevdokimov, Alexander V.; Smith, James L.; Oxley, Jimmie C.

2016-11-01

Efforts to analyze trace levels of cyclic peroxides by liquid chromatography/mass spectrometry gave evidence that acetonitrile suppressed ion formation. Further investigations extended this discovery to ketones, linear peroxides, esters, and possibly many other types of compounds, including triazole and menadione. Direct ionization suppression caused by acetonitrile was observed for multiple adduct types in both electrospray ionization and atmospheric pressure chemical ionization. The addition of only 2% acetonitrile significantly decreased the sensitivity of analyte response. Efforts to identify the mechanism were made using various nitriles. The ion suppression was reduced by substitution of an acetonitrile hydrogen with an electron-withdrawing group, but was exacerbated by electron-donating or steric groups adjacent to the nitrile. Although current theory does not explain this phenomenon, we propose that polar interactions between the various functionalities and the nitrile may be forming neutral aggregates that manifest as ionization suppression.

Density, Velocity and Ionization Structure in Accretion-Disc Winds

NASA Technical Reports Server (NTRS)

Sonneborn, George (Technical Monitor); Long, Knox

2004-01-01

This was a project to exploit the unique capabilities of FUSE to monitor variations in the wind- formed spectral lines of the luminous, low-inclination, cataclysmic variables(CV) -- RW Sex. (The original proposal contained two additional objects but these were not approved.) These observations were intended to allow us to determine the relative roles of density and ionization state changes in the outflow and to search for spectroscopic signatures of stochastic small-scale structure and shocked gas. By monitoring the temporal behavior of blue-ward extended absorption lines with a wide range of ionization potentials and excitation energies, we proposed to track the changing physical conditions in the outflow. We planned to use a new Monte Carlo code to calculate the ionization structure of and radiative transfer through the CV wind. The analysis therefore was intended to establish the wind geometry, kinematics and ionization state, both in a time-averaged sense and as a function of time.

Density functional study of double ionization energies

NASA Astrophysics Data System (ADS)

Chong, D. P.

2008-02-01

In this paper, double ionization energies (DIEs) of gas-phase atoms and molecules are calculated by energy difference method with density functional theory. To determine the best functional for double ionization energies, we first study 24 main group atoms in the second, third, and fourth periods. An approximation is used in which the electron density is first obtained from a density functional computation with the exchange-correlation potential Vxc known as statistical average of orbital potentials, after which the energy is computed from that density with 59 different exchange-correlation energy functionals Exc. For the 24 atoms, the two best Exc functional providing DIEs with average absolute deviation (AAD) of only 0.25eV are the Perdew-Burke-Ernzerhof functional modified by Hammer et al. [Phys. Rev. B 59, 6413 (1999)] and one known as the Krieger-Chen-Iafrate-Savin functional modified by Krieger et al. (unpublished). Surprisingly, none of the 20 available hybrid functionals is among the top 15 functionals for the DIEs of the 24 atoms. A similar procedure is then applied to molecules, with opposite results: Only hybrid functionals are among the top 15 functionals for a selection of 29molecules. The best Exc functional for the 29molecules is found to be the Becke 1997 functional modified by Wilson et al. [J. Chem. Phys. 115, 9233 (2001)]. With that functional, the AAD from experiment for DIEs of 29molecules is just under 0.5eV. If the two suspected values for C2H2 and Fe(CO)5 are excluded, the AAD improves to 0.32eV. Many other hybrid functionals perform almost as well.

Nonvolatile GaAs Random-Access Memory

NASA Technical Reports Server (NTRS)

Katti, Romney R.; Stadler, Henry L.; Wu, Jiin-Chuan

1994-01-01

Proposed random-access integrated-circuit electronic memory offers nonvolatile magnetic storage. Bits stored magnetically and read out with Hall-effect sensors. Advantages include short reading and writing times and high degree of immunity to both single-event upsets and permanent damage by ionizing radiation. Use of same basic material for both transistors and sensors simplifies fabrication process, with consequent benefits in increased yield and reduced cost.

Next generation offline approaches to trace organic compound speciation: Approaching comprehensive speciation with soft ionization and very high resolution tandem mass spectrometry

NASA Astrophysics Data System (ADS)

Khare, P.; Marcotte, A.; Sheu, R.; Ditto, J.; Gentner, D. R.

2017-12-01

Intermediate- and semi-volatile organic compounds (IVOCs and SVOCs) have high secondary organic aerosol (SOA) yields, as well as significant ozone formation potentials. Yet, their emission sources and oxidation pathways remain largely understudied due to limitations in current analytical capabilities. Online mass spectrometers are able to collect real time data but their limited mass resolving power renders molecular level characterization of IVOCs and SVOCs from the unresolved complex mixture unfeasible. With proper sampling techniques and powerful analytical instrumentation, our offline tandem mass spectrometry (i.e. MS×MS) techniques provide molecular-level and structural identification over wide polarity and volatility ranges. We have designed a novel analytical system for offline analysis of gas-phase SOA precursors collected on custom-made multi-bed adsorbent tubes. Samples are desorbed into helium via a gradual temperature ramp and sample flow is split equally for direct-MS×MS analysis and separation via gas chromatography (GC). The effluent from GC separation is split again for analysis via atmospheric pressure chemical ionization quadrupole time-of-flight mass spectrometry (APCI-Q×TOF) and traditional electron ionization mass spectrometry (EI-MS). The compounds for direct-MS×MS analysis are delivered via a transfer line maintained at 70ºC directly to APCI-Q×TOF, thus preserving the molecular integrity of thermally-labile, or other highly-reactive, organic compounds. Both our GC-MS×MS and direct-MS×MS analyses report high accuracy parent ion masses as well as information on molecular structure via MS×MS, which together increase the resolution of unidentified complex mixtures. We demonstrate instrument performance and present preliminary results from urban atmospheric samples collected from New York City with a wide range of compounds including highly-functionalized organic compounds previously understudied in outdoor air. Our work offers new insights into emerging emission sources in urban environments that can have a major impact on public health and also improves understanding of anthropogenic SOA precursor emissions.

Products and Mechanism of Aerosol Formation from the Reaction of β-Pinene with NO3 Radicals: Role of Oligomer Formation

NASA Astrophysics Data System (ADS)

Claflin, M. S.; Ziemann, P. J.

2017-12-01

Large amounts of organic nitrates have been reported in aerosol analyzed during field studies conducted around the world. Although organic nitrates can be formed in daytime from the oxidation of volatile organic compounds in the presence of NOx, it has recently been proposed that the nighttime reaction of monoterpenes with NO3 radicals may account for a substantial fraction of these compounds. While past studies have made progress quantifying the aerosol forming potential of these reactions, relatively little is known about the gas-phase oxidation mechanism, the identities of stable products, and their fate after they partition into aerosol. In an effort to better understand these reactions, we conducted environmental chamber experiments in which β-pinene was reacted with NO3 radicals and the secondary organic aerosol (SOA) that formed was analyzed online using a thermal desorption particle beam mass spectrometer and offline using a variety of methods. SOA was collected on filters, extracted, and analyzed using derivatization-spectrophotometric methods to quantify carbonyl, hydroxyl, carboxyl, nitrate, peroxide, and ester functional groups; and molecular products were identified and quantified by coupling high performance liquid chromatography with UV-Vis detection and mass spectrometry with electrospray ionization, electron ionization, and chemical ionization. We identified and quantified >98% of the products in the SOA and found that 95% were oligomers formed through hemiacetal and acetal reactions. This information was used to determine the yields of monomer building blocks, which in turn were combined with modeling to estimate branching ratios in the gas-phase oxidation reaction and timescales of oligomer formation within the aerosol. The results of this study highlight several key processes in the formation of SOA from reactions of monoterpenes with NO3 radicals: (1) alkoxy radical chemistry, including the role of ring opening through decomposition (2) particle-phase reactions and (3) formation of separate organic and aqueous phases within aerosol.

The Dissipation Range of Interstellar Turbulence

NASA Astrophysics Data System (ADS)

Spangler, Steven R.; Buffo, J. J.

2013-06-01

Turbulence may play an important role in a number of interstellar processes. One of these is heating of the interstellar gas, as the turbulent energy is dissipated and changed into thermal energy of the gas, or at least other forms of energy. There have been very promising recent results on the mechanism for dissipation of turbulence in the Solar Wind (Howes et al, Phys. Plasm. 18, 102305, 2011). In the Solar Wind, the dissipation arises because small-scale irregularities develop properties of kinetic Alfven waves, and apparently damp like kinetic Alfven waves. A property of kinetic Alfven waves is that they become significantly compressive on size scales of order the ion Larmor radius. Much is known about the plasma properties of ionized components of interstellar medium such as HII regions and the Diffuse Ionized Gas (DIG) phase, including information on the turbulence in these media. The technique of radio wave scintillations can yield properties of HII region and DIG turbulence on scales of order the ion Larmor radius, which we refer to as the dissipation scale. In this paper, we collect results from a number of published radio scattering measurements of interstellar turbulence on the dissipation scale. These studies show evidence for a spectral break on the dissipation scale, but no evidence for enhanced compressibility of the fluctuations. The simplest explanation of our result is that turbulence in the ionized interstellar medium does not possess properties of kinetic Alfven waves. This could point to an important difference with Solar Wind turbulence. New observations, particularly with the Very Long Baseline Array (VLBA) could yield much better measurements of the power spectrum of interstellar turbulence in the dissipation range. This research was supported at the University of Iowa by grants AST09-07911 and ATM09-56901 from the National Science Foundation.

New Evidence for Efficient Collisionless Heating of Electrons at the Reverse Shock of a Young Supernova Remnant

NASA Technical Reports Server (NTRS)

Yamaguchi, Hiroya; Eriksen, Kristoffer A.; Badenes, Carles; Hughes, John P.; Brickhouse, Nancy S.; Foster, Adam R.; Patnaude, Daniel J.; Petre, Robert; Slane, Patrick O.; Smith, Randall K.

2013-01-01

Although collisionless shocks are ubiquitous in astrophysics, certain key aspects of them are not well understood. In particular, the process known as collisionless electron heating, whereby electrons are rapidly energized at the shock front, is one of the main open issues in shock physics. Here, we present the first clear evidence for efficient collisionless electron heating at the reverse shock of Tycho's supernova remnant (SNR), revealed by Fe K diagnostics using high-quality X-ray data obtained by the Suzaku satellite. We detect K beta (3p yields 1s) fluorescence emission from low-ionization Fe ejecta excited by energetic thermal electrons at the reverse shock front, which peaks at a smaller radius than Fe K alpha (2p yields 1s) emission dominated by a relatively highly ionized component. Comparisons with our hydrodynamical simulations imply instantaneous electron heating to a temperature 1000 times higher than expected from Coulomb collisions alone. The unique environment of the reverse shock, which is propagating with a high Mach number into rarefied ejecta with a low magnetic field strength, puts strong constraints on the physical mechanism responsible for this heating and favors a cross-shock potential created by charge deflection at the shock front. Our sensitive observation also reveals that the reverse shock radius of this SNR is about 10% smaller than the previous measurement using the Fe K alpha morphology from the Chandra observations. Since strong Fe K beta fluorescence is expected only from low-ionization plasma where Fe ions still have many 3p electrons, this feature is key to diagnosing the plasma state and distribution of the immediate postshock ejecta in a young SNR.

Air ionizer application for electrostatic discharge (ESD) dust removal in automotive painting industry

NASA Astrophysics Data System (ADS)

Yosri, M. H.; Muhamad, P.; Ismail, M. A.; Yatim, N. H. M.

2018-01-01

Dust and fiber have been identified among the highest contributor for the defect in automotive painting line with range from 40% to 50% of total defect breakdown. Eventually, those defects will effect on both visual appearance and also the performance of the parts. In addition, the significance of controlling dust in an assembly line is crucial in order to maintain the quality of the product, part performance yield and effect on workers’ health [1]. By considering the principle and technology applied in electronic clean room technology, the ionizer have been introduce to control dust contamination in automotive painting line. The first auto maker industry whom found the effectiveness of the clean room application to reduce the defect and production line downtime was Chrysler [2]. By doing so, it’s allowed the transmission plant to offer 50 000 mile guarantee on the transmission systems. The main objective of this research is to verify the effectiveness of ionizer device in order to reduce the rejection contribute by dust and fiber particle in the automotive painting line. Towards the main objective, a few sub areas will be explored, as a supporting factor to ensure the result gain from this study is solid and constructive. The experiment start by verifying the electrostatic value of the raw material (substrate) before and after the ionizer treatment. From here the correlation of the electrostatic value generated by the raw material that effect to production pass rate can be explored. At the meantime, the performance of the production pass rate after the ionizer treatment which related to the painted surface area can be determined.

Three-Dimensional Electromagnetic Monte Carlo Particle-in-Cell Simulations of Critical Ionization Velocity Experiments in Space

NASA Technical Reports Server (NTRS)

Wang, J.; Biasca, R.; Liewer, P. C.

1996-01-01

Although the existence of the critical ionization velocity (CIV) is known from laboratory experiments, no agreement has been reached as to whether CIV exists in the natural space environment. In this paper we move towards more realistic models of CIV and present the first fully three-dimensional, electromagnetic particle-in-cell Monte-Carlo collision (PIC-MCC) simulations of typical space-based CIV experiments. In our model, the released neutral gas is taken to be a spherical cloud traveling across a magnetized ambient plasma. Simulations are performed for neutral clouds with various sizes and densities. The effects of the cloud parameters on ionization yield, wave energy growth, electron heating, momentum coupling, and the three-dimensional structure of the newly ionized plasma are discussed. The simulations suggest that the quantitative characteristics of momentum transfers among the ion beam, neutral cloud, and plasma waves is the key indicator of whether CIV can occur in space. The missing factors in space-based CIV experiments may be the conditions necessary for a continuous enhancement of the beam ion momentum. For a typical shaped charge release experiment, favorable CIV conditions may exist only in a very narrow, intermediate spatial region some distance from the release point due to the effects of the cloud density and size. When CIV does occur, the newly ionized plasma from the cloud forms a very complex structure due to the combined forces from the geomagnetic field, the motion induced emf, and the polarization. Hence the detection of CIV also critically depends on the sensor location.

Strong-field approximation for ionization of a diatomic molecule by a strong laser field. II. The role of electron rescattering off the molecular centers

NASA Astrophysics Data System (ADS)

Busuladžić, M.; Gazibegović-Busuladžić, A.; Milošević, D. B.; Becker, W.

2008-09-01

The strong-field approximation for ionization of diatomic molecules by a strong laser field [D. B. Milošević, Phys. Rev. A 74, 063404 (2006)] is generalized to include rescattering of the ionized electron wave packet off the molecular centers (the electron’s parent ion or the second atom). There are four rescattering contributions to the ionization rate, which are responsible for the high-energy plateau in the electron spectra and which interfere in a complicated manner. The spectra are even more complicated due to the different symmetry properties of the atomic orbitals of which a particular molecular orbital consists. Nevertheless, a comparatively simple condition emerges for the destructive interference of all these contributions, which yields a curve in the (Epf,θ) plane. Here θ is the electron emission angle and Epf is the electron kinetic energy. The resulting suppression of the rescattering plateau can be strong and affect a large area of the (Epf,θ) plane, depending on the orientation of the molecule. We illustrate this using the examples of the 3σg molecular orbital of N2 and the 1πg molecular orbital of O2 for various orientations of these molecules with respect to the laser polarization axis. For N2 , for perpendicular orientation and the equilibrium internuclear distance R0 , we find that the minima of the ionization rate form the curve Epfcos2θ=π2/(2R02) in the (Epf,θ) plane. For O2 the rescattering plateau is absent for perpendicular orientation.

Calculation on spectrum of direct DNA damage induced by low-energy electrons including dissociative electron attachment.

PubMed

Liu, Wei; Tan, Zhenyu; Zhang, Liming; Champion, Christophe

2017-03-01

In this work, direct DNA damage induced by low-energy electrons (sub-keV) is simulated using a Monte Carlo method. The characteristics of the present simulation are to consider the new mechanism of DNA damage due to dissociative electron attachment (DEA) and to allow determining damage to specific bases (i.e., adenine, thymine, guanine, or cytosine). The electron track structure in liquid water is generated, based on the dielectric response model for describing electron inelastic scattering and on a free-parameter theoretical model and the NIST database for calculating electron elastic scattering. Ionization cross sections of DNA bases are used to generate base radicals, and available DEA cross sections of DNA components are applied for determining DNA-strand breaks and base damage induced by sub-ionization electrons. The electron elastic scattering from DNA components is simulated using cross sections from different theoretical calculations. The resulting yields of various strand breaks and base damage in cellular environment are given. Especially, the contributions of sub-ionization electrons to various strand breaks and base damage are quantitatively presented, and the correlation between complex clustered DNA damage and the corresponding damaged bases is explored. This work shows that the contribution of sub-ionization electrons to strand breaks is substantial, up to about 40-70%, and this contribution is mainly focused on single-strand break. In addition, the base damage induced by sub-ionization electrons contributes to about 20-40% of the total base damage, and there is an evident correlation between single-strand break and damaged base pair A-T.

Direct calibration of a reference standard against the air kerma strength primary standard, at 192Ir HDR energy.

PubMed

Rajan, K N Govinda; Selvam, T Palani; Bhatt, B C; Vijayam, M; Patki, V S; Vinatha; Pendse, A M; Kannan, V

2002-04-07

The primary standard of low air kerma rate sources or beams, maintained at the Radiological Standards Laboratory (RSL) of the Bhabha Atomic Research Centre (BARC), is a 60 cm3 spherical graphite ionization chamber. A 192Ir HDR source was standardized at the hospital site in units of air kerma strength (AKS) using this primary standard. A 400 cm3 bakelite chamber, functioning as a reference standard at the RSL for a long period, at low air kerma rates (compared to external beam dose rates), was calibrated against the primary standard. It was seen that the primary standard and the reference standard, both being of low Z, showed roughly the same scatter response and yielded the same calibration factor for the 400 cm3 reference chamber, with or without room scatter. However, any likelihood of change in the reference chamber calibration factor would necessitate the re-transport of the primary standard to the hospital site for re-calibration. Frequent transport of the primary standard can affect the long-term stability of the primary standard, due to its movement or other extraneous causes. The calibration of the reference standard against the primary standard at the RSL, for an industrial type 192Ir source maintained at the laboratory, showed excellent agreement with the hospital calibration, making it possible to check the reference chamber calibration at RSL itself. Further calibration procedures have been developed to offer traceable calibration of the hospital well ionization chambers.

Radiation-induced synthesis of poly(acrylic acid) nanogels

NASA Astrophysics Data System (ADS)

Matusiak, Malgorzata; Kadlubowski, Slawomir; Ulanski, Piotr

2018-01-01

Nanogel is a two-component system of a diameter in the range of tens of nanometers, consisting of an intramolecularly crosslinked polymer chain and solvent, typically water, filling the space between segments of the macromolecule. Microgels are bigger than nanogels and their size range is between 100 nm to 100 μm. One of the methods used for synthesizing nanogels is linking the segments of a single macromolecule with the use of ionizing radiation, by intramolecular recombination of radiation-generated polymer radicals. The main advantage of this technique is absence of monomers, catalysts, surfactants or crosslinking agents. This method is an interesting alternative way of synthesizing polymeric carriers for biomedical applications. The aim of the study was radiation synthesis and characterization of poly(acrylic acid) - PAA - nanogels and microgels. The physico-chemical properties were described by determination of weight-average molecular weight and dimensions (radius of gyration, hydrodynamic radius) of the nanogels and microgels. Influence of polymer concentration and dose on these parameters was analyzed. Adjusting the PAA concentration and absorbed dose, one can control the molecular weight and dimensions of nanogels. The solutions of PAA were irradiated with two sources of ionizing radiation: γ-source and electron accelerator. The former method yields mainly microgels due to prevailing intermolecular crosslinking, while the latter promotes intramolecular recombination of PAA-derived radicals and in consequence formation of nanogels. In the future radiation-synthesized PAA nanogels, after functionalization, will be tested as carriers for delivering radionuclides to the tumor cells.

Asteroseismic Investigations of the Binary System HD 176465

NASA Astrophysics Data System (ADS)

Gai, Ning; Basu, Sarbani; Tang, Yanke

2018-04-01

HD 176465 is a binary system for which both components are solar-like pulsators and oscillation frequencies were observed by the Kepler mission. In this paper, we have modeled the asteroseismic and spectroscopic data of the stars, and have determined their convection-zone helium abundances using the signatures left by the He II ionization zone on the mode frequencies. As expected, we find that the components of the binary are of the same age within uncertainties (3.087 ± 0.580 Gyr and 3.569 ± 0.912 Gyr); they also have the same initial helium abundance (Y init = 0.253 ± 0.006 and 0.254 ± 0.008). Their current metallicity ([Fe/H] = ‑0.275 ± 0.04 and ‑0.285 ± 0.04) is also the same within errors. Fits to the signature of the He II acoustic glitch yield current helium abundances of Y A = 0.224 ± 0.006 and Y B = 0.233 ± 0.008 for the two components. Analyzing the complete ensemble of models generated for this investigation, we find that both the amplitude and acoustic depth of the glitch signature arising from the second helium ionization zone and the base of the convection zone (CZ) are functions of mass. We show that the acoustic depths of these glitches are positively correlated with each other. The analysis can help us to detect the internal structure and constrain the chemical compositions.

Enhanced characterization of singly protonated phosphopeptide ions by femtosecond laser-induced ionization/dissociation tandem mass spectrometry (fs-LID-MS/MS).

PubMed

Smith, Scott A; Kalcic, Christine L; Safran, Kyle A; Stemmer, Paul M; Dantus, Marcos; Reid, Gavin E

2010-12-01

To develop an improved understanding of the regulatory role that post-translational modifications (PTMs) involving phosphorylation play in the maintenance of normal cellular function, tandem mass spectrometry (MS/MS) strategies coupled with ion activation techniques such as collision-induced dissociation (CID) and electron-transfer dissociation (ETD) are typically employed to identify the presence and site-specific locations of the phosphate moieties within a given phosphoprotein of interest. However, the ability of these techniques to obtain sufficient structural information for unambiguous phosphopeptide identification and characterization is highly dependent on the ion activation method employed and the properties of the precursor ion that is subjected to dissociation. Herein, we describe the application of a recently developed alternative ion activation technique for phosphopeptide analysis, termed femtosecond laser-induced ionization/dissociation (fs-LID). In contrast to CID and ETD, fs-LID is shown to be particularly suited to the analysis of singly protonated phosphopeptide ions, yielding a wide range of product ions including a, b, c, x, y, and z sequence ions, as well as ions that are potentially diagnostic of the positions of phosphorylation (e.g., 'a(n)+1-98'). Importantly, the lack of phosphate moiety losses or phosphate group 'scrambling' provides unambiguous information for sequence identification and phosphorylation site characterization. Therefore, fs-LID-MS/MS can serve as a complementary technique to established methodologies for phosphoproteomic analysis. Copyright © 2010. Published by Elsevier Inc.

Particle-in-cell simulations of the critical ionization velocity effect in finite size clouds

NASA Technical Reports Server (NTRS)

Moghaddam-Taaheri, E.; Lu, G.; Goertz, C. K.; Nishikawa, K. - I.

1994-01-01

The critical ionization velocity (CIV) mechanism in a finite size cloud is studied with a series of electrostatic particle-in-cell simulations. It is observed that an initial seed ionization, produced by non-CIV mechanisms, generates a cross-field ion beam which excites a modified beam-plasma instability (MBPI) with frequency in the range of the lower hybrid frequency. The excited waves accelerate electrons along the magnetic field up to the ion drift energy that exceeds the ionization energy of the neutral atoms. The heated electrons in turn enhance the ion beam by electron-neutral impact ionization, which establishes a positive feedback loop in maintaining the CIV process. It is also found that the efficiency of the CIV mechanism depends on the finite size of the gas cloud in the following ways: (1) Along the ambient magnetic field the finite size of the cloud, L (sub parallel), restricts the growth of the fastest growing mode, with a wavelength lambda (sub m parallel), of the MBPI. The parallel electron heating at wave saturation scales approximately as (L (sub parallel)/lambda (sub m parallel)) (exp 1/2); (2) Momentum coupling between the cloud and the ambient plasma via the Alfven waves occurs as a result of the finite size of the cloud in the direction perpendicular to both the ambient magnetic field and the neutral drift. This reduces exponentially with time the relative drift between the ambient plasma and the neutrals. The timescale is inversely proportional to the Alfven velocity. (3) The transvers e charge separation field across the cloud was found to result in the modulation of the beam velocity which reduces the parallel heating of electrons and increases the transverse acceleration of electrons. (4) Some energetic electrons are lost from the cloud along the magnetic field at a rate characterized by the acoustic velocity, instead of the electron thermal velocity. The loss of energetic electrons from the cloud seems to be larger in the direction of plasma drift relative to the neutrals, where the loss rate is characterized by the neutral drift velocity. It is also shown that a factor of 4 increase in the ambient plasma density, increases the CIV ionization yield by almost 2 orders of magnitude at the end of a typical run. It is concluded that a larger ambient plasma density can result in a larger CIV yield because of (1) larger seed ion production by non-CIV mechanisms, (2) smaller Alfven velocity and hence weak momentum coupling, and (3) smaller ratio of the ion beam density to the ambient ion density, and therefore a weaker modulation of the beam velocity. The simulation results are used to interpret various chemical release experiments in space.

Modeling photoionization of aqueous DNA and its components.

PubMed

Pluhařová, Eva; Slavíček, Petr; Jungwirth, Pavel

2015-05-19

Radiation damage to DNA is usually considered in terms of UVA and UVB radiation. These ultraviolet rays, which are part of the solar spectrum, can indeed cause chemical lesions in DNA, triggered by photoexcitation particularly in the UVB range. Damage can, however, be also caused by higher energy radiation, which can ionize directly the DNA or its immediate surroundings, leading to indirect damage. Thanks to absorption in the atmosphere, the intensity of such ionizing radiation is negligible in the solar spectrum at the surface of Earth. Nevertheless, such an ionizing scenario can become dangerously plausible for astronauts or flight personnel, as well as for persons present at nuclear power plant accidents. On the beneficial side, ionizing radiation is employed as means for destroying the DNA of cancer cells during radiation therapy. Quantitative information about ionization of DNA and its components is important not only for DNA radiation damage, but also for understanding redox properties of DNA in redox sensing or labeling, as well as charge migration along the double helix in nanoelectronics applications. Until recently, the vast majority of experimental and computational data on DNA ionization was pertinent to its components in the gas phase, which is far from its native aqueous environment. The situation has, however, changed for the better due to the advent of photoelectron spectroscopy in liquid microjets and its most recent application to photoionization of aqueous nucleosides, nucleotides, and larger DNA fragments. Here, we present a consistent and efficient computational methodology, which allows to accurately evaluate ionization energies and model photoelectron spectra of aqueous DNA and its individual components. After careful benchmarking, the method based on density functional theory and its time-dependent variant with properly chosen hybrid functionals and polarizable continuum solvent model provides ionization energies with accuracy of 0.2-0.3 eV, allowing for faithful modeling and interpretation of DNA photoionization. The key finding is that the aqueous medium is remarkably efficient in screening the interactions within DNA such that, unlike in the gas phase, ionization of a base, nucleoside, or nucleotide depends only very weakly on the particular DNA context. An exception is the electronic interaction between neighboring bases which can lead to sequence-specific effects, such as a partial delocalization of the cationic hole upon ionization enabled by presence of adjacent bases of the same type.

Chemo-selective high yield microwave assisted reaction turns cellulose to green chemicals.

PubMed

Hassanzadeh, Salman; Aminlashgari, Nina; Hakkarainen, Minna

2014-11-04

Exceptionally high cellulose liquefaction yields, up to 87% as calculated from the amount of solid residue, were obtained under mild conditions by utilizing the synergistic effect of microwave radiation and acid catalysis. The effect of processing conditions on degradation products was fingerprinted by rapid laser desorption ionization-mass spectrometry (LDI-MS) method. The reaction was chemo-tunable, enabling production of glucose (Glc) or levulinic acid (LeA) at significantly high selectivity and yields, the relative molar yields being up to 50 and 69%, respectively. A turning point from pure depolymerization to glucose to further degradation to levulinic acid and formic acid was observed at approximately 50% liquefaction or above 140 °C. This was accompanied by the formation of small amounts of solid spherical carbonized residues. The reaction was monitored by multiple analytical techniques. The high yields were connected to the ability of the process to break the strong secondary interactions in cellulose. The developed method has great potential for future production of green platform chemicals. Copyright © 2014 Elsevier Ltd. All rights reserved.

Improved sample utilization in thermal ionization mass spectrometry isotope ratio measurements: refined development of porous ion emitters for nuclear forensic applications

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

Baruzzini, Matthew Louis

The precise and accurate determination of isotopic composition in nuclear forensic samples is vital for assessing origin, intended use and process history. Thermal ionization mass spectrometry (TIMS) is widely accepted as the gold standard for high performance isotopic measurements and has long served as the workhorse in the isotopic ratio determination of nuclear materials. Nuclear forensic and safeguard specialists have relied heavily on such methods for both routine and atypical e orts. Despite widespread use, TIMS methods for the assay of actinide systems continue to be hindered by poor ionization e ciency, often less than tenths of a percent; themore » majority of a sample is not measured. This represents a growing challenge in addressing nextgeneration nuclear detection needs by limiting the ability to analyze ultratrace quantities of high priority elements that could potentially provide critical nuclear forensic signatures. Porous ion emitter (PIE) thermal ion sources were developed in response to the growing need for new TIMS ion source strategies for improved ionization e ciency, PIEs have proven to be simple to implement, straightforward approach to boosting ion yield. This work serves to expand the use of PIE techniques for the analysis of trace quantities of plutonium and americium. PIEs exhibited superior plutonium and americium ion yields when compared to direct lament loading and the resin bead technique, one of the most e cient methods for actinide analysis, at similar mass loading levels. Initial attempts at altering PIE composition for the analysis of plutonium proved to enhance sample utilization even further. Preliminary investigations of the instrumental fractionation behavior of plutonium and uranium analyzed via PIE methods were conducted. Data collected during these initial trial indicate that PIEs fractionate in a consistent, reproducible manner; a necessity for high precision isotope ratio measurements. Ultimately, PIEs methods were applied for the age determination of various uranium isotopic standards. PIEs did not exhibit signi cant advantages for the determination of model ages when compared to traditional laments; however, this trial was able to provide valuable insight for guiding future investigations.« less

Surface analysis under ambient conditions using plasma-assisted desorption/ionization mass spectrometry.

PubMed

Ratcliffe, Lucy V; Rutten, Frank J M; Barrett, David A; Whitmore, Terry; Seymour, David; Greenwood, Claire; Aranda-Gonzalvo, Yolanda; Robinson, Steven; McCoustra, Martin

2007-08-15

A novel plasma-assisted desorption/ionization (PADI) method that can be coupled with atmospheric pressure sampling mass spectrometry to yield mass spectral information under ambient conditions of pressure and humidity from a range of surfaces without the requirement for sample preparation or additives is reported. PADI is carried out by generating a nonthermal plasma which interacts directly with the surface of the analyte. Desorption and ionization then occur at the surface, and ions are sampled by the mass spectrometer. The PADI technique is demonstrated and compared with desorption electrospray ionization (DESI) for the detection of active ingredients in a range of over-the-counter and prescription pharmaceutical formulations, including nonsterodial anti-inflammatory drugs (mefenamic acid, Ibugel, and ibuprofen), analgesics (paracetamol, Anadin Extra), and Beecham's "all in one" cold and flu remedy. PADI has also been successfully applied to the analysis of nicotine in tobacco and thiosulfates in garlic. PADI experiments have been performed using a prototype source interfaced with a Waters Platform LCZ single-quadrupole mass spectrometer with limited modifications and a Hiden Analytical HPR-60 molecular beam mass spectrometer (MBMS). The ability of PADI to rapidly detect active ingredients in pharmaceuticals without the need for prior sample preparation, solvents, or exposed high voltages demonstrates the potential of the technique for high-throughput screening in a pharmaceutical or forensic environment.

Spectroscopic investigations of ThF and ThF+.

PubMed

Barker, Beau J; Antonov, Ivan O; Heaven, Michael C; Peterson, Kirk A

2012-03-14

The electronic spectra of ThF and ThF(+) have been examined using laser induced fluorescence and resonant two-photon ionization techniques. The results from high-level ab initio calculations have been used to guide the assignment of these data. Spectra for ThF show that the molecule has an X (2)Δ(3/2) ground state. The upper spin-orbit component, X (2)Δ(5/2) was found at an energy of 2575(15) cm(-1). The low-lying states of ThF(+) were probed using dispersed fluorescence and pulsed field ionization-zero kinetic energy (PFI-ZEKE) photoelectron spectroscopy. Vibronic progressions belonging to four electronic states were identified. The lowest energy states were clearly (1)Σ(+) and (3)Δ(1). Although the energy ordering could not be rigorously determined, the evidence favors assignment of (1)Σ(+) as the ground state. The (3)Δ(1) state, of interest for investigation of the electron electric dipole moment, is just 315.0(5) cm(-1) above the ground state. The PFI-ZEKE measurements for ThF yielded an ionization energy of 51 581(3) cm(-1). Molecular constants show that the vibrational constant increases and the bond length shortens on ionization. This is consistent with removal of a non-bonding Th-centered 6d or 7s electron. Laser excitation of ThF(+) was used to probe electronically excited states in the range of 19,000-21,500 cm(-1).

Basic poly(propylene glycols) as reference compounds for internal mass calibration in positive-ion matrix-assisted laser desorption/ionization mass spectrometry.

PubMed

Gross, Jürgen H

2017-12-01

Basic poly(propylene glycols), commercially available under the trade name Jeffamine, are evaluated for their potential use as internal mass calibrants in matrix-assisted laser desorption/ionization-time-of-flight-mass spectrometry. Due to their basic amino endgroups Jeffamines are expected to deliver [M+H] + ions in higher yields than neutral poly(propylene glycols) or poly(ethylene glycols). Aiming at accurate mass measurements and molecular formula determinations by matrix-assisted laser desorption/ionization-time-of-flight-mass spectrometry, four Jeffamines (M-600, M-2005, D-400, D-230) were thus compared. As a result, Jeffamine M-2005 is introduced as a new mass calibrant for positive-ion matrix-assisted laser desorption/ionization-time-of-flight-mass spectrometry in the range of m/z 200-1200 and the reference mass list is provided. While Jeffamine M-2005 is compatible with α-cyano-4-hydroxycinnamic acid, 2,5-dihydroxybenzoic acid, and 2-[(2 E)-3-(4- tert-butylphenyl)-2-methylprop-2-enylidene]malonitrile matrix, its use in combination with 2-[(2 E)-3-(4- tert-butylphenyl)-2-methylprop-2-enylidene]malonitrile provides best results due to low laser fluence requirements. Applications to PEG 300, PEG 600, the ionic liquid trihexyl(tetradecyl)-phosphonium tris(pentafluoroethyl)-trifluorophosphate, and [60]fullerene demonstrate mass accuracies of 2-5 ppm.