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Sample records for air molecules ionized

  1. Nonsequential double ionization of molecules

    SciTech Connect

    Prauzner-Bechcicki, Jakub S.; Sacha, Krzysztof; Zakrzewski, Jakub; Eckhardt, Bruno

    2005-03-01

    Double ionization of diatomic molecules by short linearly polarized laser pulses is analyzed. We consider the final stage of the ionization process, that is the decay of a highly excited two electron molecule, which is formed after rescattering. The saddles of the effective adiabatic potential energy close to which simultaneous escape of electrons takes place are identified. Numerical simulations of the ionization of molecules show that the process can be dominated by either sequential or nonsequential events. In order to increase the ratio of nonsequential to sequential ionizations very short laser pulses should be applied.

  2. XUV ionization of aligned molecules

    NASA Astrophysics Data System (ADS)

    Kelkensberg, F.; Rouzée, A.; Siu, W.; Gademann, G.; Johnsson, P.; Lucchini, M.; Lucchese, R. R.; Vrakking, M. J. J.

    2011-11-01

    New extreme-ultraviolet (XUV) light sources such as high-order-harmonic generation (HHG) and free-electron lasers (FELs), combined with laser-induced alignment techniques, enable novel methods for making molecular movies based on measuring molecular frame photoelectron angular distributions. Experiments are presented where CO2 molecules were impulsively aligned using a near-infrared laser and ionized using femtosecond XUV pulses obtained by HHG. Measured electron angular distributions reveal contributions from four orbitals and the onset of the influence of the molecular structure.

  3. XUV ionization of aligned molecules

    SciTech Connect

    Kelkensberg, F.; Siu, W.; Gademann, G.; Rouzee, A.; Vrakking, M. J. J.; Johnsson, P.; Lucchini, M.; Lucchese, R. R.

    2011-11-15

    New extreme-ultraviolet (XUV) light sources such as high-order-harmonic generation (HHG) and free-electron lasers (FELs), combined with laser-induced alignment techniques, enable novel methods for making molecular movies based on measuring molecular frame photoelectron angular distributions. Experiments are presented where CO{sub 2} molecules were impulsively aligned using a near-infrared laser and ionized using femtosecond XUV pulses obtained by HHG. Measured electron angular distributions reveal contributions from four orbitals and the onset of the influence of the molecular structure.

  4. Measuring Air-Ionizer Output

    NASA Technical Reports Server (NTRS)

    Lonborg, J. O.

    1985-01-01

    Test apparatus checks ion content of airstream from commercial air ionizer. Apparatus ensures ion output is sufficient to neutralize static charges in electronic assembly areas and concentrations of positive and negative ions are balanced.

  5. Microwave remote sensing of ionized air.

    SciTech Connect

    Liao, S.; Gopalsami, N.; Heifetz, A.; Elmer, T.; Fiflis, P.; Koehl, E. R.; Chien, H. T.; Raptis, A. C.

    2011-07-01

    We present observations of microwave scattering from ambient room air ionized with a negative ion generator. The frequency dependence of the radar cross section of ionized air was measured from 26.5 to 40 GHz (Ka-band) in a bistatic mode with an Agilent PNA-X series (model N5245A) vector network analyzer. A detailed calibration scheme is provided to minimize the effect of the stray background field and system frequency response on the target reflection. The feasibility of detecting the microwave reflection from ionized air portends many potential applications such as remote sensing of atmospheric ionization and remote detection of radioactive ionization of air.

  6. The Multiphoton Multiple Ionization of Molecules.

    NASA Astrophysics Data System (ADS)

    Hatherly, P. A.

    Available from UMI in association with The British Library. The multiphoton multiple ionization of a number of molecular systems has been studied using the picosecond laser facility at the Rutherford Appleton Laboratory. The laser produced 0.6ps pulses at 600nm, and 6ps at 248nm when used in conjunction with an excimer laser. The focused intensity in each case was >=q10 ^{15}W/cm^2 . A time of flight mass spectrometer designed and built at Reading University was capable of ion kinetic energy measurement, permitting the molecular dissociation dynamics to be investigated. One major question approached concerned the mode of multiphoton ionization of xenon. Specifically, does the ionization proceed in a sequential (single electron) or a collective (many electron) manner? To this end, experiments were performed with the isoelectronic molecule hydrogen iodide. The results, which were interpreted in terms of a Coulomb explosion mechanism, demonstrated the process to be sequential, rather than collective. Similar experiments on the isoelectronic pair, nitrogen and carbon monoxide tended to confirm this conclusion. These molecules were also studied at a number of laser wavelengths and pulse widths. Although the wavelength was found to have a minimal effect, the pulse width was of great importance. The results for hydrogen and deuterium contrasted with these results for other molecules, in that the energies could not be reconciled with a Coulomb explosion mechanism. Rather, dissociative autoionization or neutral dissociation followed by ionization of the atoms were considered to be the dominant processes. Finally, the existence of high energy protons (~eq100eV) from residual hydrocarbons in the vacuum chamber lead to a study of the alkanes from butane to dodecane. At 600nm, 0.6ps pulse width, the fragment energies were found to vary linearly with carbon chain length. At 248nm, 5ps though, only low energy protons were observed, independent of chain length.

  7. Ionization of glycerin molecule by electron impact

    NASA Astrophysics Data System (ADS)

    Zavilopulo, A. N.; Shpenik, O. B.; Markush, P. P.; Kontrosh, E. E.

    2015-07-01

    The methods and results of studying the yield of positive ions produced due to direct and dissociative electron impact ionization of the glycerin molecule are described. The experiment is carried out using two independent setups, namely, a setup with a monopole mass spectrometer employing the method of crossing electron and molecular beams and a setup with a hypocycloidal electron spectrometer with the gas-filled cell. The mass spectra of the glycerin molecule are studied in the range of mass numbers of 10-95 amu at various temperatures. The energy dependences of the effective cross sections of the glycerin molecular ions produced by a monoenergetic electron beam are obtained and analyzed; using these dependences, the appearance energies of fragment ions are determined. The dynamics of the glycerin molecule fragment ions formation is investigated in the temperature range of 300-340 K.

  8. Dissociative Ionization of Aromatic and Heterocyclic Molecules

    NASA Technical Reports Server (NTRS)

    Huo, Winifred M.

    2003-01-01

    Space radiation poses a major health hazard to humans in space flight. The high-energy charged particles in space radiation ranging from protons to high atomic number, high-energy (HZE) particles, and the secondary species they produce, attack DNA, cells, and tissues. Of the potential hazards, long-term health effects such as carcinogenesis are likely linked to the DNA lesions caused by secondary electrons in the 1 - 30 eV range. Dissociative ionization (DI) is one of the electron collision processes that can damage the DNA, either directly by causing a DNA lesion, or indirectly by producing radicals and cations that attack the DNA. To understand this process, we have developed a theoretical model for DI. Our model makes use of the fact that electron motion is much faster than nuclear motion and assumes DI proceeds through a two-step process. The first step is electron-impact ionization resulting in a particular state of the molecular ion in the geometry of the neutral molecule. In the second step the ion undergoes unimolecular dissociation. Thus the DI cross section sigma(sup DI)(sub a) for channel a is given by sigma(sup DI)(sub a) = sigma(sup I)(sub a) P(sub D) with sigma(sup I)(sub a) the ionization cross section of channel a and P(sub D) the dissociation probability. This model has been applied to study the DI of H2O, NH3, and CH4, with results in good agreement with experiment. The ionization cross section sigma(sup I)(sub a) was calculated using the improved binary encounter-dipole model and the unimolecular dissociation probability P(sub D) obtained by following the minimum energy path determined by the gradients and Hessians of the electronic energy with respect to the nuclear coordinates of the ion. This model is used to study the DI from the low-lying channels of benzene and pyridine to understand the different product formation in aromatic and heterocyclic molecules. DI study of the DNA base thymine is underway. Solvent effects will also be discussed.

  9. Ionization and dissociation dynamics of molecules in strong laser fields

    NASA Astrophysics Data System (ADS)

    Lai, Wei

    The fast advancement of ultrashort-pulsed high-intensity laser technology allows for generating an electric field equivalent to the Coulomb field inside an atom or a molecule (e.g., EC=5.14x109 V/cm at the 1s orbit radius a0=0.0529 nm of the hydrogen atom, which corresponds to an intensity of 3.54x1016 W/cm2). Atoms and molecules exposed in such a field will easily be ionized, as the external field is strong enough to remove the electrons from the core. This is usually referred to "strong field". Strong fields provide a new tool for studying the interaction of atoms and molecules with light in the nonlinear nonperturbative regime. During the past three decades, significant progress has been made in the strong field science. Today, most phenomena involving atoms in strong fields have been relatively well understood by the single-active-electron (SAE) approximation. However, the interpretation of these responses in molecules has encountered great difficulties. Not like atoms that only undergo excitation and ionization, various dissociation channels accompanying excitation and ionization can occur in molecules during the laser pulse interaction, which imparts further complexity to the study of molecules in strong fields. Previous studies have shown that molecules can behave significantly different from rare gas atoms in phenomena as simple as single and double ionization. Molecular dissociation following ionization also presents challenges in strong fields compared to what we have learned in the weak-field regime. This dissertation focuses on experimental studies on ionization and dissociation of some commonly-seen small molecules in strong laser fields. Previous work of molecules in strong fields will be briefly reviewed, particularly on some open questions about multiple dissociation channels, nonsequential double ionization, enhanced ionization and molecular alignment. The identification of various molecular dissociation channels by recent experimental technical

  10. Fragmentation of the POPOP molecule by electron-impact ionization

    NASA Astrophysics Data System (ADS)

    Romanova, L. G.; Zavilopulo, A. N.; Shpenik, O. B.; Kukhto, A. V.; Agafonova, A. S.

    2008-07-01

    Single and dissociative ionizations of the POPOP molecule by electron impact in the gas phase are studied using mass spectroscopy. Fragmentation pathways of the molecule are proposed taking into account the common system of conjugated π-electrons and heteroatoms in the POPOP molecule. The appearance thresholds for certain fragments of the molecule are determined based on experimentally measured ionization cross sections as functions of the ionizing electron energy. An ion with m/z = 144 [C9H6ON]+ that is complementary to a fragment with m/z = 220 [C13H10ON]+ (present in the NIST mass spectrum database) is found for the first time in the mass spectrum of POPOP. Its appearance threshold is determined (Eap = 9.48 eV).

  11. Isotope Effect in Tunneling Ionization of Neutral Hydrogen Molecules

    NASA Astrophysics Data System (ADS)

    Wang, X.; Xu, H.; Atia-Tul-Noor, A.; Hu, B. T.; Kielpinski, D.; Sang, R. T.; Litvinyuk, I. V.

    2016-08-01

    It has been recently predicted theoretically that due to nuclear motion light and heavy hydrogen molecules exposed to strong electric field should exhibit substantially different tunneling ionization rates [O. I. Tolstikhin, H. J. Worner, and T. Morishita, Phys. Rev. A 87, 041401(R) (2013)]. We studied that isotope effect experimentally by measuring relative ionization yields for each species in a mixed H2/D2 gas jet interacting with intense femtosecond laser pulses. In a reaction microscope apparatus, we detected ionic fragments from all contributing channels (single ionization, dissociation, and sequential double ionization) and determined the ratio of total single ionization yields for H2 and D2 . The measured ratio agrees quantitatively with the prediction of the generalized weak-field asymptotic theory in an apparent failure of the frozen-nuclei approximation.

  12. Isotope Effect in Tunneling Ionization of Neutral Hydrogen Molecules.

    PubMed

    Wang, X; Xu, H; Atia-Tul-Noor, A; Hu, B T; Kielpinski, D; Sang, R T; Litvinyuk, I V

    2016-08-19

    It has been recently predicted theoretically that due to nuclear motion light and heavy hydrogen molecules exposed to strong electric field should exhibit substantially different tunneling ionization rates [O. I. Tolstikhin, H. J. Worner, and T. Morishita, Phys. Rev. A 87, 041401(R) (2013)]. We studied that isotope effect experimentally by measuring relative ionization yields for each species in a mixed H_{2}/D_{2} gas jet interacting with intense femtosecond laser pulses. In a reaction microscope apparatus, we detected ionic fragments from all contributing channels (single ionization, dissociation, and sequential double ionization) and determined the ratio of total single ionization yields for H_{2} and D_{2}. The measured ratio agrees quantitatively with the prediction of the generalized weak-field asymptotic theory in an apparent failure of the frozen-nuclei approximation. PMID:27588855

  13. Isotope Effect in Tunneling Ionization of Neutral Hydrogen Molecules.

    PubMed

    Wang, X; Xu, H; Atia-Tul-Noor, A; Hu, B T; Kielpinski, D; Sang, R T; Litvinyuk, I V

    2016-08-19

    It has been recently predicted theoretically that due to nuclear motion light and heavy hydrogen molecules exposed to strong electric field should exhibit substantially different tunneling ionization rates [O. I. Tolstikhin, H. J. Worner, and T. Morishita, Phys. Rev. A 87, 041401(R) (2013)]. We studied that isotope effect experimentally by measuring relative ionization yields for each species in a mixed H_{2}/D_{2} gas jet interacting with intense femtosecond laser pulses. In a reaction microscope apparatus, we detected ionic fragments from all contributing channels (single ionization, dissociation, and sequential double ionization) and determined the ratio of total single ionization yields for H_{2} and D_{2}. The measured ratio agrees quantitatively with the prediction of the generalized weak-field asymptotic theory in an apparent failure of the frozen-nuclei approximation.

  14. A multiphoton ionization technique for the determination of the ionization threshold of molecules in fluid media

    SciTech Connect

    Faidas, H.; Christophorou, L.G.

    1987-01-01

    A new laser-induced multiphoton conductivity technique for the determination of the ionization threshold of molecules in fluids (liquids and dense gases) is described. Results are presented and discussed on aromatic molecules in nonpolar fluids. 2 refs., 1 fig., 1 tab.

  15. Laser-induced air ionization microscopy

    NASA Astrophysics Data System (ADS)

    Zhao, Y.; Zhang, N.; Yang, J.; Zhu, X.

    2006-06-01

    A nonlinear scanning imaging method is introduced that uses the highly localized air ionization initiated by photoelectrons from the sample surface under irradiation of femtosecond laser pulses as the microprobe. This type of microscopy with realizable subdiffraction spatial resolution has the unique advantages of being highly sensitive to both elemental and topographical properties of the samples of interest. Microscopic images of a femtosecond laser ablated micropattern, the cross section and the side view profile of an optical fiber, and a fresh mulberry leaf are obtained with this imaging technique, which demonstrate this technique's broad applicability in microscopic studies of different materials.

  16. Ionization of water molecules by fast charged projectiles

    SciTech Connect

    Dubois, A.; Carniato, S.; Fainstein, P. D.; Hansen, J. P.

    2011-07-15

    Single-ionization cross sections of water molecules colliding with fast protons are calculated from lowest-order perturbation theory by taking all electrons and molecular orientations consistently into account. Explicit analytical formulas based on the peaking approximation are obtained for differential ionization cross sections with the partial contribution from the various electron orbitals accounted for. The results, which are in very good agreement with total and partial cross sections at high electron and projectile energies, display a strong variation on molecular orientation and molecular orbitals.

  17. Multielectron effects in strong field ionization of molecules

    NASA Astrophysics Data System (ADS)

    Jaron-Becker, Agnieszka; Xia, Yuqing

    2014-05-01

    Multielectron effects are studied for strong field ionization of di- and polyatomic molecules at their equilibrium geometries, using time dependent density functional theory. Strong field ionization of molecules have been previously often analyzed using ``single active electron'' (SAE) approximation based theories such as for example Intense Field Many Body S-matrix Theory and typically the contributions from inner valence orbitals and multielectron effects were concluded to be of less importance. For several di- and polyatomic molecules we show that ionization rate from inner valence orbitals can increase dramatically due to a novel resonant coupling which influences the molecular dynamics. We discuss the dependence of the results on the orientation of the molecules and laser parameters. Moreover we show how such a mechanism can lead to localization of electron depending on the symmetry of the orbitals involved. Finally, we propose how the novel mechanism can be observed experimentally and show how the multi-electron effects can help explain several experimental results which have shown disagreement with SAE approximation based theories. Supported by NSF (Grants No. PHY-1068706 and PHY-1125844).

  18. Frustrated double ionization in two-electron triatomic molecules

    NASA Astrophysics Data System (ADS)

    Chen, A.; Price, H.; Staudte, A.; Emmanouilidou, A.

    2016-10-01

    Using a semiclassical model, we investigate frustrated double ionization (FDI) in D3+ , a two-electron triatomic molecule, when driven by an intense, linearly polarized, near-infrared (800 nm) laser field. We compute the kinetic energy release of the nuclei and find a good agreement between experiment and our model. We explore the two pathways of FDI and show that, with increasing field strength, over-the-barrier ionization overtakes tunnel ionization as the underlying mechanism of FDI. Moreover, we compute the angular distribution of the ion fragments for FDI and identify a feature that can potentially be observed experimentally and is a signature of only one of the two pathways of FDI.

  19. Experimental Resonance Enhanced Multiphoton Ionization (REMPI) studies of small molecules

    NASA Technical Reports Server (NTRS)

    Dehmer, J. L.; Dehmer, P. M.; Pratt, S. T.; Ohalloran, M. A.; Tomkins, F. S.

    1987-01-01

    Resonance enhanced multiphoton ionization (REMPI) utilizes tunable dye lasers to ionize an atom or molecule by first preparing an excited state by multiphoton absorption and then ionizing that state before it can decay. This process is highly selective with respect to both the initial and resonant intermediate states of the target, and it can be extremely sensitive. In addition, the products of the REMPI process can be detected as needed by analyzing the resulting electrons, ions, fluorescence, or by additional REMPI. This points to a number of exciting opportunities for both basic and applied science. On the applied side, REMPI has great potential as an ultrasensitive, highly selective detector for trace, reactive, or transient species. On the basic side, REMPI affords an unprecedented means of exploring excited state physics and chemistry at the quantum-state-specific level. An overview of current studies of excited molecular states is given to illustrate the principles and prospects of REMPI.

  20. 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.

  1. Structure factors for tunneling ionization rates of diatomic molecules

    SciTech Connect

    Saito, Ryoichi; Tolstikhin, Oleg I.; Madsen, Lars Bojer; Morishita, Toru

    2015-05-15

    Within the leading-order, single-active-electron, and frozen-nuclei approximation of the weak-field asymptotic theory, the rate of tunneling ionization of a molecule in an external static uniform electric field is determined by the structure factor for the highest occupied molecular orbital. We present the results of systematic calculations of structure factors for 40 homonuclear and heteronuclear diatomic molecules by the Hartree–Fock method using a numerical grid-based approach implemented in the program X2DHF.

  2. Atmospheric Ionizing Radiation (AIR) Project Review

    NASA Technical Reports Server (NTRS)

    Singleterry, R. C., Jr.; Wilson, J. W.; Whitehead, A. H.; Goldhagen, P. E.

    1999-01-01

    The National Council on Radiation Protection and Measurement (NCRP) and the National Academy of Science (NAS) established that the uncertainty in the data and models associated with the high-altitude radiation environment could and should be reduced. In response, the National Aeronautics and Space Administration (NASA) and the U.S. Department of Energy Environmental Measurements Laboratory (EML) created the Atmospheric Ionizing Radiation (AIR) Project under the auspices of the High Speed Research (HSR) Program Office at the Langley Research Center. NASA's HSR Program was developed to address the potential of a second-generation supersonic transport. A critical element focussed on the environmental issues, including the threat to crew and passengers posed by atmospheric radiation. Various international investigators were solicited to contribute instruments to fly on an ER-2 aircraft at altitudes similar to those proposed for the High Speed Civil Transport (HSCT). A list of participating investigators, their institutions, and instruments with quantities measured is presented. The flight series took place at solar minimum (radiation maximum) with northern, southern, and east/west flights. The investigators analyzed their data and presented preliminary results at the AIR Workshop in March, 1998. A review of these results are included.

  3. Microwave Triggered Laser Ionization of Air

    NASA Astrophysics Data System (ADS)

    Vadiee, Ehsan; Prasad, Sarita; Jerald Buchenauer, C.; Schamiloglu, Edl

    2012-10-01

    The goal of this work is to study the evolution and dynamics of plasma expansion when a high power microwave (HPM) pulse is overlapped in time and space on a very small, localized region of plasma formed by a high energy laser pulse. The pulsed Nd:YAG laser (8 ns, 600mJ, repetition rate 10 Hz) is focused to generate plasma filaments in air with electron density of 10^17/cm^3. When irradiated with a high power microwave pulse these electrons would gain enough kinetic energy and further escalate avalanche ionization of air due to elastic electron-neutral collisions thereby causing an increased volumetric discharge region. An X-band relativistic backward wave oscillator(RBWO) at the Pulsed Power,Beams and Microwaves laboratory at UNM is constructed as the microwave source. The RBWO produces a microwave pulse of maximum power 400 MW, frequency of 10.1 GHz, and energy of 6.8 Joules. Special care is being given to synchronize the RBWO and the pulsed laser system in order to achieve a high degree of spatial and temporal overlap. A photodiode and a microwave waveguide detector will be used to ensure the overlap. Also, a new shadowgraph technique with a nanosecond time resolution will be used to detect changes in the shock wave fronts when the HPM signal overlaps the laser pulse in time and space.

  4. Overview of Atmospheric Ionizing Radiation (AIR)

    NASA Technical Reports Server (NTRS)

    Wilson, J. W.; Maiden, D. L.; Goldhagen, P.; Tai, H.; Shinn, J. L.

    2003-01-01

    The SuperSonic Transport (SST) development program within the US was based at the Langley Research Center as was the Apollo radiation testing facility (Space Radiation Effects Laboratory) with associated radiation research groups. It was natural for the issues of the SST to be first recognized by this unique combination of research programs. With a re-examination of the technologies for commercial supersonic flight and the possible development of a High Speed Civil Transport (HSCT), the remaining issues of the SST required resolution. It was the progress of SST radiation exposure research program founded by T. Foelsche at the Langley Research Center and the identified remaining issues after that project over twenty-five years ago which became the launch point of the current atmospheric ionizing radiation (AIR) research project. Added emphasis to the need for reassessment of atmospheric radiation resulted from the major lowering of the recommended occupational exposure limits, the inclusion of aircrew as radiation workers, and the recognition of civil aircrew as a major source of occupational exposures. Furthermore, the work of Ferenc Hajnal of the Environmental Measurements Laboratory brought greater focus to the uncertainties in the neutron flux at high altitudes. A re-examination of the issues involved was committed at the Langley Research Center and by the National Council on Radiation Protection (NCRP). As a result of the NCRP review, a new flight package was assembled and flown during solar minimum at which time the galactic cosmic radiation is at a maximum (June 1997). The present workshop is the initial analysis of the new data from that flight. The present paper is an overview of the status of knowledge of atmospheric ionizing radiations. We will re-examine the exposures of the world population and examine the context of aircrew exposures with implications for the results of the present research. A condensed version of this report was given at the 1998

  5. Electron-induced ionization and dissociative ionization of iron pentacarbonyl molecules

    NASA Astrophysics Data System (ADS)

    Lacko, Michal; Papp, Peter; Wnorowski, Karol; Matejčík, Štefan

    2015-03-01

    Electron ionization (EI) and dissociative ionization (DI) of Iron pentacarbonyl molecule (Fe(CO)5) was studied using a crossed molecular and electron beam mass spectrometry technique. Positive ions FeO(CO)+, FeC(CO)2+ and CO+ of Fe(CO)5 were detected for the first time. We have determined the experimental appearance energies of positive ions, the thresholds for dissociative reactions, the experimental bond dissociation energies for (CO)nFe+-CO bond breaks (for n = 4,..., 0) and their average value for Fe-C bond energy 1.25 eV in Fe(CO)5+. We have performed extensive density functional theory (DFT) studies of the ground states of neutral molecule and fragments 1 A1' Fe(CO)5, 3B1 Fe(CO)4, 3A1Fe(CO)3, 3∑g Fe(CO)2, 3 ∑FeCO as well as positive ions 2A1 Fe(CO)5+, 4A1 Fe(CO)4+, 4A1 Fe(CO)3+, 4∑g Fe(CO)2+ and 4 ∑ FeCO+. The structures and energies of the states have beendetermined and the calculated bond dissociation energies (BDEs) were compared with present experiments as well as with previous works. Contribution to the Topical Issue "Elementary Processes with Atoms and Molecules in Isolated and Aggregated States", edited by Friedrich Aumayr, Bratislav Marinkovic, Stefan Matejick, John Tanis and Kurt H. Becker.

  6. Mass spectrometry of solid samples in open air using combined laser ionization and ambient metastable ionization

    NASA Astrophysics Data System (ADS)

    He, X. N.; Xie, Z. Q.; Gao, Y.; Hu, W.; Guo, L. B.; Jiang, L.; Lu, Y. F.

    2012-01-01

    Mass spectrometry of solid samples in open air was carried out using combined laser ionization and metastable ionization time-of-flight mass spectrometry (LI-MI-TOFMS) in ambient environment for qualitative and semiquantitative (relative analyte information, not absolute information) analysis. Ambient metastable ionization using a direct analysis in realtime (DART) ion source was combined with laser ionization time-of-flight mass spectrometry (LI-TOFMS) to study the effects of combining metastable and laser ionization. A series of metallic samples from the National Institute of Standards and Technology (NIST 494, 495, 498, 499, and 500) and a pure carbon target were characterized using LI-TOFMS in open air. LI-MI-TOFMS was found to be superior to laser-induced breakdown spectroscopy (LIBS). Laser pulse energies between 10 and 200 mJ at the second harmonic (532 nm) of an Nd:YAG laser were applied in the experiment to obtain a high degree of ionization in plasmas. Higher laser pulse energy improves signal intensities of trace elements (such as Fe, Cr, Mn, Ni, Ca, Al, and Ag). Data were analyzed by numerically calculating relative sensitivity coefficients (RSCs) and limit of detections (LODs) from mass spectrometry (MS) and LIBS spectra. Different parameters, such as boiling point, ionization potential, RSC, LOD, and atomic weight, were shown to analyze the ionization and MS detection processes in open air.

  7. Unrestricted release measurements with ambient air ionization monitors

    SciTech Connect

    MacArthur, D.; Gunn, R.; Dockray, T.; Luff, C.

    1999-03-01

    Radiation monitoring systems based on the long-range alpha detection (LRAD) technique, such as the BNFL Instruments IonSens{trademark}, provide a single contamination measurement for an entire object rather than the more familiar individual readings for smaller surface areas. The LRAD technique relies on the ionization of ambient air molecules by alpha particles, and the subsequent detection of these ions, rather than direct detection of the alpha particles themselves. A single monitor can detect all of the ions produced over a large object and report a total contamination level for the entire surface of that object. However, both the unrestricted release limits specified in USDOE Order 5400.5 (and similar documents in other countries), and the definitions of radioactive waste categories, are stated in terms of contamination per area. Thus, conversion is required between the total effective contamination as measured by the LRAD-based detector and the allowable release limits. In addition, since the release limits were not written assuming an averaging detector system, the method chosen to average the assumed contamination over the object can have a significant impact on the effective sensitivity of the detector.

  8. Active Experiments on Artificial Air Ionization to Check the Physical Mechanism of Air Electrification by Radon in Seismically Active Area

    NASA Astrophysics Data System (ADS)

    Pulinets, S. A.; Pokhmelnykh, L. A.; Domingues, M.; Bisiacchi, G.

    2005-05-01

    The air ionization in troposphere leads to formation of the large charged clusters of the aerosol size due to water molecules attachment to the new formed ions. This process have several consequences leading to the changes of the air conductivity, formation of large scale space charges and large scale electric field, changes of the air temperature and relative humidity. All these effects were observed experimentally within the interval of two weeks before the strong earthquakes such as Colima earthquake in Mexico (M7.8) on 22 of January 2003 or Parkfield earthquake in USA (M6) on 28 of September 2004. In the case of earthquakes the atmosphere electricity modification is ascribed to the radon ionization and the effects are calculated within the frame of the seismo-ionosphere coupling model. But there are very few systematic sources of the radon monitoring, so the real check of the model is better possible within the frame of the controlled active experiment. Such experiments of the artificial ionization were conducted in Mexico using the large wire antennas producing the air ionization by applying the large electric potential (~ 40 kV) to the elevated circular thin wire of ~ 100 m diameter. It was demonstrated that such impact on the atmosphere can create the effects of the meteorological scale producing the artificial clouds (and rains), and even modify the large scale atmospheric formations as typhoons. Results of the theoretical estimations and active experiments will be demonstrated.

  9. Second-order Born approximation for the ionization of molecules by electron and positron impact

    SciTech Connect

    Dal Cappello, C.; Rezkallah, Z.; Houamer, S.; Charpentier, I.; Hervieux, P. A.; Ruiz-Lopez, M. F.; Dey, R.; Roy, A. C.

    2011-09-15

    Second-order Born approximation is applied to study the ionization of molecules. The initial and final states are described by single-center wave functions. For the initial state a Gaussian wave function is used while for the ejected electron it is a distorted wave. Results of the present model are compared with recent (e,2e) experiments on the water molecule. Preliminary results are also presented for the ionization of the thymine molecule by electrons and positrons.

  10. Fragmentation of Small Molecules by Photo-Double Ionization

    NASA Astrophysics Data System (ADS)

    Osipov, Timur

    2008-05-01

    Molecular structure, formation, breakup pathways and recombination formed the subject of many theoretical and experimental studies. Among molecular species like H2, CO, N2, O2 recently great attention has been paid to the dynamics of the fragmentations and rearrangements of C2H2 molecule. Nature's smallest stable hydrocarbon, the symmetric linear acetylene molecule, C2H2, is an important polyatomic system for the study of photo initiated processes. Important features of the intramolecular dynamics in neutral acetylene have been revealed over many years through numerous spectroscopic studies. More recently, the availability of synchrotron radiation and intense laser sources has lead to intriguing studies of the ionization, isomerization and breakup dynamics of acetylene ions. Of particular interest are the yields into the symmetric (CH^+/CH^+), deprotonation (HCC^+/H^+) and quasi-symmetric (HHC^+/C^+) channels, the latter involving isomerization from the neutral acetylene structure into the vinylidene configuration prior to breakup. One expects that the products of dissociation, their kinetic energy releases (KER) and the isomerization times will depend on the particular initial electronic states of the dication involved, but such detailed information has heretofore not been available. We will present the results of the experiment where the dication of acetylene is prepared by Auger decay following core-level X-ray photoionization. Cold Target Recoil Ion Momentum Spectroscopy technique was used to measure the corresponding 3d momentum vectors of Auger electrons and recoil ions in coincidence. We will show that this experimental approach, in combination with ab initio quantum mechanical calculations, can yield a comprehensive map of the two-body dissociation pathways including transition through different electronic energy surfaces, barriers to direct dissociation and the associated rearrangement channels. Work done in collaboration with T. Rescigno, T. Weber, S

  11. Microwave diagnostics of laser-induced avalanche ionization in air

    SciTech Connect

    Zhang Zhili; Shneider, Mikhail N.; Miles, Richard B.

    2006-10-01

    This work presents a simplified model of microwave scattering during the avalanche ionization stage of laser breakdown and corresponding experimental results of microwave scattering from laser breakdown in room air. The model assumes and measurements confirm that the breakdown regime can be viewed as a point dipole scatterer of the microwave radiation and thus directly related to the time evolving number of electrons. The delay between the laser pulse and the rise of the microwave scattering signal is a direct measure of the avalanche ionization process.

  12. Electron Impact Ionization Cross Sections and Rate Coefficients for Single Carbon Freon Molecules

    NASA Astrophysics Data System (ADS)

    Pal, Satyendra; Kumar, Neeraj

    2015-09-01

    Single carbon Freon molecules or chlorofluorocarbons (CFCs) are important industrial material with wide-ranging applications as refrigerant, aerosol propellant and semiconductor etchant, etc. The large-scale industrial consumption is of particular environmental concern because of its potential for ozone destruction in the stratosphere. In the present work, we have extended and generalized the modified Jain-Khare (JK) semi-empirical formalism for the evaluation of the total ionization cross sections corresponding to the formation of the cations in the electron impact ionization of molecules to the electron impact ionization of single carbon freon molecules, viz. CFCl3, CF2Cl2 and CF3Cl. The integral partial and the total ionization cross sections as function of incident electron energy are evaluated in the energy range varying from ionization threshold to 1000 eV. In absence of available differential cross sections, the corresponding derived partial and total ionization cross sections revealed a reasonably good agreement with the experimental and theoretical data, wherever available. In addition to the differential and integral ionization cross sections, we have also calculated the ionization rate coefficients using the evaluated partial ionization cross sections and the Maxwell-Boltzmann distribution as a function of electron temperature/energy. The work is supported by DST, New Delhi, India.

  13. Double ionization of water molecules induced by swift protons

    NASA Astrophysics Data System (ADS)

    Tavares, A. C.; Luna, H.; Wolff, W.; Montenegro, E. C.

    2015-09-01

    Experimental cross sections for single and double ionization of H2O by swift H+ with energy ranging from 0.3 to 2.0 MeV are reported. In this energy range the ionization is the dominant collision process and charge transfer reactions can be disregarded. A multihit coincidence technique is used to measure the H++OH+ and H++O+ fragmentation channels. Single- and double-hit differential measurements together with a semiempirical calculation allow separating quantitatively the prompt and Auger-like decay contributions to fragmentation following a vacancy in the 2 a1 molecular orbital. Concerning the double-ionization channel, it is found that for lower energies the mechanism of a sequential double-electron removal, known as TS2, dominates. For energies above above 750 keV/u ionization resulting from a single vacancy followed by an Auger like deexcitation takes over the TS2, becoming the main contribution to the double-ionization cross section. Our results are compared to the electron-impact data within the same velocity range and also with theoretical calculations available in the literature.

  14. Determination of Energy-Transfer Distributions in Ionizing Ion-Molecule Collisions.

    PubMed

    Maclot, S; Delaunay, R; Piekarski, D G; Domaracka, A; Huber, B A; Adoui, L; Martín, F; Alcamí, M; Avaldi, L; Bolognesi, P; Díaz-Tendero, S; Rousseau, P

    2016-08-12

    The ionization and fragmentation of the nucleoside thymidine in the gas phase has been investigated by combining ion collision with state-selected photoionization experiments and quantum chemistry calculations. The comparison between the mass spectra measured in both types of experiments allows us to accurately determine the distribution of the energy deposited in the ionized molecule as a result of the collision. The relation of two experimental techniques and theory shows a strong correlation between the excited states of the ionized molecule with the computed dissociation pathways, as well as with charge localization or delocalization. PMID:27563959

  15. Determination of Energy-Transfer Distributions in Ionizing Ion-Molecule Collisions

    NASA Astrophysics Data System (ADS)

    Maclot, S.; Delaunay, R.; Piekarski, D. G.; Domaracka, A.; Huber, B. A.; Adoui, L.; Martín, F.; Alcamí, M.; Avaldi, L.; Bolognesi, P.; Díaz-Tendero, S.; Rousseau, P.

    2016-08-01

    The ionization and fragmentation of the nucleoside thymidine in the gas phase has been investigated by combining ion collision with state-selected photoionization experiments and quantum chemistry calculations. The comparison between the mass spectra measured in both types of experiments allows us to accurately determine the distribution of the energy deposited in the ionized molecule as a result of the collision. The relation of two experimental techniques and theory shows a strong correlation between the excited states of the ionized molecule with the computed dissociation pathways, as well as with charge localization or delocalization.

  16. Phase-dependent ionization suppression in atoms and molecules

    NASA Astrophysics Data System (ADS)

    Foote, David B.; Lee, Jane; Chen, Guan-Yeu; Hill, Wendell T., III

    2014-05-01

    Evolving methods in ultrafast laser pulse shaping allow a more complete investigation into the role of both the carrier envelope phase (CEP) and chirp in quantum control experiments. Recent investigations suggest that phase is one of the key parameters in quantum control mechanisms. To reveal the nature of the role phase plays we have employed a phase-only spatial light modulator (SLM) to shape 800 nm, sub-60 fs transform-limited pulses into a pair of transform-limited pulses (~ 60 fs) where the relative phase and temporal separation can be adjusted independently. At a fixed temporal separation, approximately three times the pulse width, the ionization signal was measured as the phase was varied over 2 π + . The ionization signals show a periodic dependence on the phase; at specific phase values the second pulse was rendered impotent, leading to an ionization suppression in both atomic and molecular systems. When the temporal separation was adjusted, a propensity for the relative phase between the two carriers to remain fixed was observed. This suggests that the phase difference could be responsible for ``trapping'' population in states inaccessible to ionization. These results and their implication will be presented in this poster.

  17. New model for electron-impact ionization cross sections of atoms and molecules

    NASA Astrophysics Data System (ADS)

    Kim, Y.-K.; Hwang, W.; Rudd, M. E.

    1996-07-01

    A new theoretical model for electron-impact ionization cross sections for atoms and molecules is presented. The new model combines the binary-encounter theory and the Bethe theory for electron-impact ionization, and uses minimal theoretical data for the ground state of the target atom or molecule. Two versions of the model are presented. The first one, the Binary-Encounter-Dipole (BED) model, requires the knowledge of continuum oscillator strengths and produces the differential ionization cross section, i.e., energy distribution of ejected electrons. The differential cross section is then integrated over the ejected electron energy to obtain the total ionization cross section. The second version, the Binary-Encounter-Bethe (BEB) model, assumes a simple form of the continuum oscillator strength to obtain a compact and analytic form of the total ionization cross section. We found that both the BED and BEB models provide total ionization cross sections from threshold to several keV in incident energy within 5% to 15% of known experimental data for many neutral targets. The total ionization cross sections are expressed in compact analytic expressions suitable for use in modeling, e.g., of plasmas and radiation effects. We found that the BEB model is particularly effective in estimating total ionization cross sections of complex molecules.

  18. Ionization Properties of Molecules Commonly Used for Plasma Processing of Semi-Conductors

    NASA Technical Reports Server (NTRS)

    Srivastava, S. K.

    2000-01-01

    Two types of processes are involved in plasma processing of semi-conductors. They are: plasma etching or cleaning and plasma deposition of the semi-conducting materials. For plasma etching of semi-conductors mostly halogen containing gases are used as additives to gases such as O2 and N2. For plasma deposition gases such as C2H2, SiH4, Si2H6 have been tested in the past. For an optimal performance of a reactor it is important to model the plasma. In this modeling effort electron impact excitation and ionization cross sections play a central role. For ionization balance calculations values of ionization cross sections are needed. Ion molecule reactions determine the ultimate composition of the plasma. Recently it has been discovered that the by products of many of these plasmas are per fluro hydrocarbons (PFCs) which are highly infrared absorbing species and have long life times in the atmosphere. They cause global warming. A lot of research is being pursued at the present time to find alternative molecules which do not produce global warming gases as the and product of the plasma processing reactor. There is also interest in the ionization and dissociative ionization properties of these molecules from the point view of the plasma abatement of the pollutant gases at the exhaust of the semi-conductor processing reactors. At the conference ionization and dissociative ionization properties of some of these molecules will be presented.

  19. Electron ionization dynamics of N2 and O2 molecules: Velocity-map imaging

    NASA Astrophysics Data System (ADS)

    Bull, James N.; Lee, Jason W. L.; Vallance, Claire

    2015-02-01

    This paper reports a crossed-beam velocity-map imaging study into the electron ionization dynamics of jet-cooled N2 and O2 molecules at electron collision energies from 35 to 100 eV. The use of velocity-map imaging detection provides insight into the detailed ionization dynamics through the dimension of the product ion kinetic energy associated with impulsive dissociation. In particular, "mesoscopic" cross sections corresponding to ionization from manifolds of energetically close states converging to the same dissociation asymptote are reported for a number of single-ionization channels. In addition, a range of double-ionization cross sections have been characterized, including those yielding X2 2 + dications. These are found to be in excellent agreement with other cross sections determined in coincidence measurements. This agreement supports a meaningful and accurate determination of the single-ionization channels.

  20. Auger spectrum of a water molecule after single and double core ionization.

    PubMed

    Inhester, L; Burmeister, C F; Groenhof, G; Grubmüller, H

    2012-04-14

    The high intensity of free electron lasers opens up the possibility to perform single-shot molecule scattering experiments. However, even for small molecules, radiation damage induced by absorption of high intense x-ray radiation is not yet fully understood. One of the striking effects which occurs under intense x-ray illumination is the creation of double core ionized molecules in considerable quantity. To provide insight into this process, we have studied the dynamics of water molecules in single and double core ionized states by means of electronic transition rate calculations and ab initio molecular dynamics (MD) simulations. From the MD trajectories, photoionization and Auger transition rates were computed based on electronic continuum wavefunctions obtained by explicit integration of the coupled radial Schrödinger equations. These rates served to solve the master equations for the populations of the relevant electronic states. To account for the nuclear dynamics during the core hole lifetime, the calculated electron emission spectra for different molecular geometries were incoherently accumulated according to the obtained time-dependent populations, thus neglecting possible interference effects between different decay pathways. We find that, in contrast to the single core ionized water molecule, the nuclear dynamics for the double core ionized water molecule during the core hole lifetime leaves a clear fingerprint in the resulting electron emission spectra. The lifetime of the double core ionized water was found to be significantly shorter than half of the single core hole lifetime.

  1. Auger spectrum of a water molecule after single and double core ionization

    SciTech Connect

    Inhester, L.; Burmeister, C. F.; Groenhof, G.; Grubmueller, H.

    2012-04-14

    The high intensity of free electron lasers opens up the possibility to perform single-shot molecule scattering experiments. However, even for small molecules, radiation damage induced by absorption of high intense x-ray radiation is not yet fully understood. One of the striking effects which occurs under intense x-ray illumination is the creation of double core ionized molecules in considerable quantity. To provide insight into this process, we have studied the dynamics of water molecules in single and double core ionized states by means of electronic transition rate calculations and ab initio molecular dynamics (MD) simulations. From the MD trajectories, photoionization and Auger transition rates were computed based on electronic continuum wavefunctions obtained by explicit integration of the coupled radial Schroedinger equations. These rates served to solve the master equations for the populations of the relevant electronic states. To account for the nuclear dynamics during the core hole lifetime, the calculated electron emission spectra for different molecular geometries were incoherently accumulated according to the obtained time-dependent populations, thus neglecting possible interference effects between different decay pathways. We find that, in contrast to the single core ionized water molecule, the nuclear dynamics for the double core ionized water molecule during the core hole lifetime leaves a clear fingerprint in the resulting electron emission spectra. The lifetime of the double core ionized water was found to be significantly shorter than half of the single core hole lifetime.

  2. Theoretical Calculation for the Ionization of Molecules by Short Strong Laser Pulses

    SciTech Connect

    Nagy, L.; Borbely, S.

    2011-10-03

    We have developed several calculation methods for the ionization of atoms and molecules by strong and ultrashort laser pulses, based on the numerical solution of the time dependent Schroedinger equation (TDSE) in the momentum space. We have performed calculations within the strong field approximation (Volkov) and using iterative and direct methods for solving the TDSE. The investigated molecules are H{sub 2}{sup +} and H{sub 2}O. In case of the ionization of diatomic molecules the interference effects in the ejected electron spectra due to the coherent addition of the waves associated to the electrons ejected from the vicinity of different nuclei were also analysed.

  3. Photon Energy Deposition in Strong-Field Single Ionization of Multielectron Molecules

    NASA Astrophysics Data System (ADS)

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

    2016-09-01

    Molecules exposed to strong laser fields may coherently absorb multiple photons and deposit the energy into electrons and nuclei, triggering the succeeding dynamics as the primary stage of the light-molecule interaction. We experimentally explore the electron-nuclear sharing of the absorbed photon energy in above-threshold multiphoton single ionization of multielectron molecules. Using CO as a prototype, vibrational and orbital resolved electron-nuclear sharing of the photon energy is observed. Different from the simplest one- or two-electron systems, the participation of the multiple orbitals and the coupling of various electronic states in the strong-field ionization and dissociation processes alter the photon energy deposition dynamics of the multielectron molecule. The population of numerous vibrational states of the molecular cation as the energy reservoir in the ionization process plays an important role in photon energy sharing between the emitted electron and the nuclear fragments.

  4. Photon Energy Deposition in Strong-Field Single Ionization of Multielectron Molecules.

    PubMed

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

    2016-09-01

    Molecules exposed to strong laser fields may coherently absorb multiple photons and deposit the energy into electrons and nuclei, triggering the succeeding dynamics as the primary stage of the light-molecule interaction. We experimentally explore the electron-nuclear sharing of the absorbed photon energy in above-threshold multiphoton single ionization of multielectron molecules. Using CO as a prototype, vibrational and orbital resolved electron-nuclear sharing of the photon energy is observed. Different from the simplest one- or two-electron systems, the participation of the multiple orbitals and the coupling of various electronic states in the strong-field ionization and dissociation processes alter the photon energy deposition dynamics of the multielectron molecule. The population of numerous vibrational states of the molecular cation as the energy reservoir in the ionization process plays an important role in photon energy sharing between the emitted electron and the nuclear fragments. PMID:27636472

  5. Ionization of oriented carbonyl sulfide molecules by intense circularly polarized laser pulses

    SciTech Connect

    Dimitrovski, Darko; Abu-samha, Mahmoud; Madsen, Lars Bojer; Filsinger, Frank; Meijer, Gerard; Kuepper, Jochen; Holmegaard, Lotte; Kalhoej, Line; Nielsen, Jens H.; Stapelfeldt, Henrik

    2011-02-15

    We present combined experimental and theoretical results on strong-field ionization of oriented carbonyl sulfide molecules by circularly polarized laser pulses. The obtained molecular frame photoelectron angular distributions show pronounced asymmetries perpendicular to the direction of the molecular electric dipole moment. These findings are explained by a tunneling model invoking the laser-induced Stark shifts associated with the dipoles and polarizabilities of the molecule and its unrelaxed cation. The focus of the present article is to understand the strong-field ionization of one-dimensionally-oriented polar molecules, in particular asymmetries in the emission direction of the photoelectrons. In the following article [Phys. Rev. A 83, 023406 (2011)] the focus is to understand strong-field ionization from three-dimensionally-oriented asymmetric top molecules, in particular the suppression of electron emission in nodal planes of molecular orbitals.

  6. Photon Energy Deposition in Strong-Field Single Ionization of Multielectron Molecules.

    PubMed

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

    2016-09-01

    Molecules exposed to strong laser fields may coherently absorb multiple photons and deposit the energy into electrons and nuclei, triggering the succeeding dynamics as the primary stage of the light-molecule interaction. We experimentally explore the electron-nuclear sharing of the absorbed photon energy in above-threshold multiphoton single ionization of multielectron molecules. Using CO as a prototype, vibrational and orbital resolved electron-nuclear sharing of the photon energy is observed. Different from the simplest one- or two-electron systems, the participation of the multiple orbitals and the coupling of various electronic states in the strong-field ionization and dissociation processes alter the photon energy deposition dynamics of the multielectron molecule. The population of numerous vibrational states of the molecular cation as the energy reservoir in the ionization process plays an important role in photon energy sharing between the emitted electron and the nuclear fragments.

  7. Laser Induced Tunnel Ionization and Electron Density Evolution in Air

    NASA Astrophysics Data System (ADS)

    Tiwari, Pawan K.; Brussaard, G. J. H.; Wiel, M. J. v. d.; Tripathi, V. K.

    2005-08-01

    An indigenously built Ti:sapphire laser system delivering 50 mJ, 100 fs pulses at a repetition rate of 10 Hz, is employed to tunnel ionize air at 1 atm pressure and form a plasma channel. The laser is line focused using a cylindrical lens to a spot size of 20 μm× 1 mm. A folded wave interferometry is used to deduce the radial electron density profile by measuring the phase shift and employing Abel inversion. The maximum value of chord-integrated electron density and radial electron density are estimated to be approximately equal to 3.0× 1016 cm-2 and 4.0× 1018 cm-3 respectively with density scale length of 20 μm. These results have been theoretically interpreted by developing a unified formalism of tunnel ionization. The experimental results are in reasonable agreement with the theory.

  8. Air flow assisted ionization for remote sampling of ambient mass spectrometry and its application.

    PubMed

    He, Jiuming; Tang, Fei; Luo, Zhigang; Chen, Yi; Xu, Jing; Zhang, Ruiping; Wang, Xiaohao; Abliz, Zeper

    2011-04-15

    Ambient ionization methods are an important research area in mass spectrometry (MS) analysis. Under ambient conditions, the gas flow and atmospheric pressure significantly affect the transfer and focusing of ions. The design and implementation of air flow assisted ionization (AFAI) as a novel and effective, remote sampling method for ambient mass spectrometry are described herein. AFAI benefits from a high extracting air flow rate. A systematic investigation of the extracting air flow in the AFAI system has been carried out, and it has been demonstrated not only that it plays a role in the effective capture and remote transport of charged droplets, but also that it promotes desolvation and ion formation, and even prevents ion fragmentation during the ionization process. Moreover, the sensitivity of remote sampling ambient MS analysis was improved significantly by the AFAI method. Highly polar and nonpolar molecules, including dyes, pharmaceutical samples, explosives, drugs of abuse, protein and volatile compounds, have been successfully analyzed using AFAI-MS. The successful application of the technique to residue detection on fingers, large object analysis and remote monitoring in real time indicates its potential for the analysis of a variety of samples, especially large objects. The ability to couple this technique with most commercially available MS instruments with an API interface further enhances its broad applicability.

  9. Double Ionization of Hydrogen Molecule by Intense Attosecond Laser Pulses

    NASA Astrophysics Data System (ADS)

    Lee, Teck-Ghee; Pindzola, M. S.; Robicheaux, F.

    2010-03-01

    Time-dependent close-coupling calculations within the fixed nuclei approximation are carried out for the double ionization of H2 induced by an intense attosecond laser pulse at a photon energy of 40 eV. We consider here the two-photon absorption processes and examine the response of the ejected electrons, particularly the single- and the double-electron energy distributions, to linearly and circularly polarized pulse at laser intensities between 10^15 W/cm^2 and 10^16 W/cm^2. We find that, for both the linearly and circularly polarized pulses, sequential peaks and non-sequential wells appear in both the single- and double-electron energy distributions that are generally akin to the analogous two electrons photoemission processes in He atom driven by a linearly polarized intense attosecond pulse [1,2]. Furthermore, a clear signature of the sequential double-electron above threshold ionization process can be seen in the single- and double-electron energy distributions when a linearly polarized pulse is being used.[4pt] [1] I. F. Barna, J. Wang, and J. Burgdorfer, Phys. Rev. A. 73, 023402 (2006) [0pt] [2] T-G Lee, M. S. Pindzola and F. Robicheaux, Phys. Rev. A. 79, 053420 (2009)

  10. Multiphoton ionization and third-harmonic generation in atoms and molecules

    SciTech Connect

    Compton, R.N.

    1982-01-01

    Resonantly enhanced multiphoton ionization (REMPI) provides a powerful new method for investigating atomic and molecular energy levels. The method is particularly useful in discovering and characterizing certain optically forbidden transitions. The method is particularly well suited for studying Rydberg transitions in molecules and is experimentally easier than the traditional use of far ultraviolet radiation in conventional spectroscopy. Research on multiphoton ionization and third-harmonic generation is reviewed. (WHK)

  11. UV and VUV Ionization of Organic Molecules, Clusters, and Complexes

    NASA Astrophysics Data System (ADS)

    Marksteiner, Markus; Haslinger, Philipp; Sclafani, Michele; Ulbricht, Hendrik; Arndt, Markus

    2009-08-01

    The generation of organic particle beams is studied in combination with photoionization using UV radiation at 266 nm and vacuum ultraviolet (VUV) light at 157 nm. Single-photon ionization with pulsed VUV light turns out to be sensitive enough to detect various large neutral biomolecular complexes ranging from metal-amino acid complexes to nucleotide clusters and aggregates of polypeptides. Different biomolecular clusters are shown to exhibit rather specific binding characteristics with regard to the various metals that are codesorbed in the source. We also find that the ion signal of gramicidin can be increased by a factor of 15 when the photon energy is increased from 4.66 to 7.9 eV.

  12. Enhancements of rescattered electron yields in above-threshold ionization of molecules

    SciTech Connect

    Cornaggia, C.

    2010-11-15

    In above-threshold ionization of rare-gas atoms, photoelectron spectra recorded in the 10{sup 13}-10{sup 14} W cm{sup -2} range exhibit enhancements in the rescattering plateaus that do not have a unified theoretical interpretation yet. Here an experimental search for such enhancements is reported in simple molecules with ionization potentials near those of rare-gas atoms such as H{sub 2} and N{sub 2} for argon and O{sub 2} for xenon, and in other molecules such as CO{sub 2} and N{sub 2}O. Only H{sub 2} exhibits the enhancements previously observed in atoms. The H{sub 2} particularity is interpreted in terms of its simpler ion structure and associated ionization paths compared with other molecules.

  13. Imaging of the umbrella motion and tunneling in ammonia molecules by strong-field ionization

    NASA Astrophysics Data System (ADS)

    Förster, Johann; Plésiat, Etienne; Magaña, Álvaro; Saenz, Alejandro

    2016-10-01

    The geometry-dependent ionization behavior of ammonia molecules is investigated. Different theoretical approaches for obtaining the ionization yield are compared, all of them showing a strong dependence of the ionization yield on the inversion coordinate at long wavelengths (≥800 nm). It is shown how this effect can be exploited to create and probe nuclear wave packets in neutral ammonia using Lochfraß. Furthermore, imaging of a wave packet tunneling through the barrier of a double-well potential in real time is discussed.

  14. Complete Solution of Electronic Excitation and Ionization in Electron-Hydrogen Molecule Scattering.

    PubMed

    Zammit, Mark C; Savage, Jeremy S; Fursa, Dmitry V; Bray, Igor

    2016-06-10

    The convergent close-coupling method has been used to solve the electron-hydrogen molecule scattering problem in the fixed-nuclei approximation. Excellent agreement with experiment is found for the grand total, elastic, electronic-excitation, and total ionization cross sections from the very low to the very high energies. This shows that for the electronic degrees of freedom the method provides a complete treatment of electron scattering on molecules as it does for atoms. PMID:27341229

  15. Complete Solution of Electronic Excitation and Ionization in Electron-Hydrogen Molecule Scattering

    NASA Astrophysics Data System (ADS)

    Zammit, Mark C.; Savage, Jeremy S.; Fursa, Dmitry V.; Bray, Igor

    2016-06-01

    The convergent close-coupling method has been used to solve the electron-hydrogen molecule scattering problem in the fixed-nuclei approximation. Excellent agreement with experiment is found for the grand total, elastic, electronic-excitation, and total ionization cross sections from the very low to the very high energies. This shows that for the electronic degrees of freedom the method provides a complete treatment of electron scattering on molecules as it does for atoms.

  16. Complete solution of electronic excitation and ionization in electron-hydrogen molecule scattering

    DOE PAGES

    Zammit, Mark C.; Savage, Jeremy S.; Fursa, Dmitry V.; Bray, Igor

    2016-06-08

    The convergent close-coupling method has been used to solve the electron-hydrogen molecule scattering problem in the fixed-nuclei approximation. Excellent agreement with experiment is found for the grand total, elastic, electronic-excitation, and total ionization cross sections from the very low to the very high energies. This shows that for the electronic degrees of freedom the method provides a complete treatment of electron scattering on molecules as it does for atoms.

  17. Electron impact-induced ionization and dissociation of the freon-12 molecule

    NASA Astrophysics Data System (ADS)

    Zavilopulo, A. N.; Agafonova, A. S.; Snegurskii, A. V.

    2010-12-01

    An experimental technique is described, and the relative cross sections of the single and dissociative electron-impact ionizations of the freon-12 molecule (CCl2F2) in the near-threshold energy range are obtained. The experiment is performed on a device that provides the mass separation and recording of ions with a monopole mass spectrometer. The mass spectrum of the freon-12 molecule is measured at various ionizing-electron energies, and the relative cross sections of dissociative ionization are measured for the most intense ion fragments, including isotope-containing fragments. The threshold dependences of these cross sections are used to determine the appearance potentials of the ion fragments. The isotope shift in the thresh-old appearance energies of ion fragments [C35ClF2]+ and [C37ClF2]+ is measured for the first time.

  18. Orientation and alignment effects in electron-induced ionization of a single oriented water molecule

    SciTech Connect

    Champion, C.; Rivarola, R. D.

    2010-10-15

    We here report a theoretical study about the orientation effect on the total ionization cross sections for a single oriented water molecule. The theoretical description of the ionization process is performed within the first Born framework with a collisional system including an initial state composed of a projectile and a water target molecule described by a plane wave and an accurate one-center molecular wave function, respectively, and a final state constituted by a slow ejected electron represented by a Coulomb wave and a scattered (fast) electron projectile described by a plane wave. Secondary electron energetic distributions as well as total cross sections are then compared for particular target configurations pointing out strong alignment and orientation effects on the description of the ionization process.

  19. Ultrafast ionization and fragmentation dynamics of molecules at high x-ray intensity

    NASA Astrophysics Data System (ADS)

    Son, Sang-Kil

    2016-05-01

    X-ray free-electron lasers (XFEL) open a new era in science and technology, offering many unique opportunities that have not been conceivable with conventional light sources. Because of their very high x-ray photon fluence within very short pulse duration, materials interacting with XFEL undergo significant radiation damage -- they possibly become highly ionized and then explode. To comprehend underlying physics, it is crucial to understand detailed ionization and fragmentation dynamics of atoms and molecules during intense XFEL pulses. We have developed the XMOLECULE toolkit to describe molecular x-ray-induced processes and to simulate radiation damage dynamics of molecules. In this talk, I will present a theoretical framework of XFEL-matter interaction, namely x-ray multiphoton absorption. Then I will discuss recent results of ultrafast x-ray-induced explosion of methyl iodide (CH3 I) molecules. Charge state distribution and kinetic energy releases of fragments are calculated to probe ionization and fragmentation dynamics, and compared with recent experimental results. It will be demonstrated that ionization of heavy-atom-containing molecules at high x-ray intensity is much enhanced in comparison with the isolated atomic case, due to ultrafast charge rearrangement during x-ray multiphoton absorption.

  20. Multiphoton and tunneling ionization probability of atoms and molecules in an intense laser field

    NASA Astrophysics Data System (ADS)

    Zhao, Song-Feng; Liu, Lu; Zhou, Xiao-Xin

    2014-02-01

    We theoretically studied ionization of atoms exposed to an intense laser field by using three different methods, i.e., the numerical solution of the single-active-electron approximation based time-dependent Schrödinger equation (SAE-TDSE), the Perelomov-Popov-Terent'ev (PPT) model, and the Ammosov-Delone-Krainov (ADK) model. The ionization of several linear molecules in a strong laser field is also investigated with the molecular ADK (MO-ADK) and the molecular PPT (MO-PPT) model. We show that the ionization probability from the PPT and the MO-PPT model agrees well with the corresponding SAE-TDSE result in both the multiphoton and tunneling ionization regimes. By considering the volume effect of the laser field, the ionization signal obtained from the PPT and the MO-PPT model fits well the experimental data in the whole range of the multiphoton and tunneling ionization regimes. However, both the ADK and MO-ADK models seriously underestimate the ionization probabilities (or signals) in the multiphoton regime.

  1. A mass spectrometry study of n-octane: Electron impact ionization and ion-molecule reactions

    NASA Astrophysics Data System (ADS)

    Jiao, C. Q.; DeJoseph, C. A.; Garscadden, A.

    2001-02-01

    Electron impact ionization of n-octane over an energy range of 10-70 eV and the subsequent ion-molecule reactions with the parent molecule have been studied using Fourier-transform mass spectrometry. Molecular ion and fragment ions C1+-C6+ are produced from the electron impact with a total ionization cross section of 1.4±0.2×10-15 cm2 between 60 and 70 eV. C3H7+ is the most abundant ion at most of the ionizing energies with the exception for E⩽16 eV where C6H13+ and C6H12+ are the most abundant. Among the fragment ions only C4H7+ and smaller ions react readily with the parent molecule, primarily producing C5H11+ and C4H9+, with rate coefficients of 0.32-2.4×10-9 cm3s-1. Essentially all of the ions, including the molecular ion and the large fragment ions, undergo decomposition upon collision with neutral molecules after they are kinetically excited to an energy range of 1-5 eV, forming a variety of small hydrocarbon ions. Many of the decomposition product ions in turn are capable of further reacting with n-octane. Isotope reagents have been utilized in experiments to probe the type of the ion-molecule reactions studied.

  2. On the influence of low-energy ionizing radiation on the amino acid molecule: proline

    NASA Astrophysics Data System (ADS)

    Tamuliene, Jelena; Romanova, Liudmila; Vukstich, Vasyl; Papp, Alexander; Shkurin, Serhiy; Baliulyte, Laura; Snegursky, Alexander

    2016-06-01

    New data on the electron-impact fragmentation of the amino acid proline molecule are presented as being related to the formation of the ionized products due to the influence of low-energy ionizing radiation on the above molecule. An extensive DFT-theory based on the theoretical approach enabled the main pathways of the proline molecules fragmentation to be elucidated. A series of the produced fragments have been identified. The absolute appearance energies for some of them have been both measured experimentally and calculated theoretically. The data of the experimental studies and theoretical calculations are compared and analyzed. Contribution to the Topical Issue "Low-Energy Interactions related to Atmospheric and Extreme Conditions", edited by S. Ptasinska, M. Smialek-Telega, A. Milosavljevic, B. Sivaraman.

  3. Detecting excess ionizing radiation by electromagnetic breakdown of air

    SciTech Connect

    Granatstein, Victor L.; Nusinovich, Gregory S.

    2010-09-15

    A scheme is proposed for detecting a concealed source of ionizing radiation by observing the occurrence of breakdown in atmospheric air by an electromagnetic wave whose electric field surpasses the breakdown field in a limited volume. The volume is chosen to be smaller than the reciprocal of the naturally occurring concentration of free electrons. The pulse duration of the electromagnetic wave must exceed the avalanche breakdown time (10-200 ns) and could profitably be as long as the statistical lag time in ambient air (typically, microseconds). Candidate pulsed electromagnetic sources over a wavelength range, 3 mm>{lambda}>10.6 {mu}m, are evaluated. Suitable candidate sources are found to be a 670 GHz gyrotron oscillator with 200 kW, 10 {mu}s output pulses and a Transversely Excited Atmospheric-Pressure (TEA) CO{sub 2} laser with 30 MW, 100 ns output pulses. A system based on 670 GHz gyrotron would have superior sensitivity. A system based on the TEA CO{sub 2} laser could have a longer range >100 m.

  4. Two-photon double ionization of the H2 molecule: Cross sections and amplitude analysis

    NASA Astrophysics Data System (ADS)

    Ivanov, I. A.; Kheifets, A. S.

    2013-02-01

    We perform time-dependent calculations of triply differential cross sections (TDCS) of two-photon double-electron ionization of the aligned H2 molecule. Our TDCS results for equal energy sharing between photoelectrons agree quite well with a recent time-dependent calculation by Guan [X. Guan, K. Bartschat, and B. I. Schneider, Phys. Rev. APLRAAN1050-294710.1103/PhysRevA.77.043421 77, 043421 (2008)] who employed a slightly different numerical technique. We supplement these studies by calculating TDCS at an unequal energy sharing and by generating symmetrized ionization amplitudes.

  5. Effects of autoionizing states on two-photon double ionization of the H2 molecule

    NASA Astrophysics Data System (ADS)

    Guan, Xiaoxu; Bartschat, Klaus; Schneider, Barry I.; Koesterke, Lars

    2014-04-01

    Treating the effects of autoionizing intermediate states on two-photon double ionization (DI) of the H2 molecule using time-dependent laser pulses is a significant computational challenge. Relatively long exposure times are critical to understanding the dynamics. Using the fixed-nuclei approximation, we demonstrate how the doubly excited states enhance the angle-integrated generalized cross sections in H2, and how they affect the angular distribution pattern of the ejected electrons. As the energy approaches the threshold for sequential DI, there is a sharp rise in the cross section due to virtual sequential ionization.

  6. Strong-field approximation for ionization of a diatomic molecule by a strong laser field

    SciTech Connect

    Milosevic, D. B.

    2006-12-15

    We present a theory of ionization of diatomic molecules by a strong laser field. A diatomic molecule is considered as a three-particle system, which consists of two heavy atomic (ionic) centers and an electron. After the separation of the center-of-mass coordinate, the dynamics of this system is reduced to the relative electronic and nuclear coordinates. The exact S-matrix element for ionization is presented in a form in which the laser-molecule interaction is emphasized. This form is useful for application of the molecular strong-field approximation (SFA). We introduced two forms of the molecular SFA, one with the field-free and the other with the field-dressed initial molecular bound state. We relate these two forms of our modified molecular SFA to the standard molecular SFAs, introduced previously using the length gauge and the velocity gauge. Numerical examples of the ionization rates of N{sub 2} and O{sub 2} molecules are shown and compared for all four versions of the molecular SFA and we suggest that our modified molecular SFA should be used instead of the standard molecular SFA.

  7. Enhanced ionization of the H2 molecule driven by intense ultrashort laser pulses

    NASA Astrophysics Data System (ADS)

    Dehghanian, E.; Bandrauk, A. D.; Kamta, G. Lagmago

    2010-06-01

    We report correlated two-electron ab initio calculations for the hydrogen molecule H2 in interaction with intense ultrashort laser pulses, via a solution of the full three-dimensional time-dependent Schrödinger equation. Our results for ionization and excitation probabilities (at 800 and 400 nm) as a function of internuclear distance R show strong evidence of enhanced ionization, in both single and double ionization, as well as enhanced excitation, in single and double excitation, as the internuclear distance R increases from the equilibrium value Re. The enhancement of all these molecular processes exhibits a maximum at a critical distance Rc, which can be predicted from simple electrostatic and recollision models.

  8. Ionization-site effects on the photofragmentation of chloro- and bromoacetic acid molecules

    NASA Astrophysics Data System (ADS)

    Levola, Helena; Itälä, Eero; Schlesier, Kim; Kooser, Kuno; Laine, Sanna; Laksman, Joakim; Ha, Dang Trinh; Rachlew, Elisabeth; Tarkanovskaja, Marta; Tanzer, Katrin; Kukk, Edwin

    2015-12-01

    Fragmentation of gas-phase chloro- and bromoacetic acid samples, particularly its dependency on the atomic site of the initial core ionization, was studied in photoelectron-photoion-photoion coincidence (PEPIPICO) measurements. The fragmentation was investigated after ionizing carbon 1 s and bromine 3 d or chlorine 2 p core orbitals. It was observed that the samples had many similar fragmentation pathways and that their relative weights depended strongly on the initial ionization site. Additional Auger PEPIPICO measurements revealed a clear dependence of fragment pair intensities on the kinetic energy of the emitted Auger electrons. The modeled and measured Auger electron spectra indicated that the average internal energy of the molecule was larger following the carbon 1 s core-hole decay than after the decay of the halogen core hole. This difference in the internal energies was found to be the source of the site-dependent photofragmentation behavior.

  9. Core Ionization Initiates Subfemtosecond Charge Migration in the Valence Shell of Molecules

    NASA Astrophysics Data System (ADS)

    Kuleff, Alexander I.; Kryzhevoi, Nikolai V.; Pernpointner, Markus; Cederbaum, Lorenz S.

    2016-08-01

    After the ionization of a valence electron, the created hole can migrate ultrafast from one end of the molecule to another. Because of the advent of attosecond pulse techniques, the measuring and understanding of charge migration has become a central topic in attosecond science. Here, we pose the hitherto unconsidered question whether ionizing a core electron will also lead to charge migration. It is found that the created hole in the core stays put, but in response to this hole interesting electron dynamics takes place which can lead to intense charge migration in the valence shell. This migration is typically faster than that after the ionization of a valence electron and transpires on a shorter time scale than the natural decay of the core hole by the Auger process, making the subject very challenging to attosecond science.

  10. Air flow-assisted ionization imaging mass spectrometry method for easy whole-body molecular imaging under ambient conditions.

    PubMed

    Luo, Zhigang; He, Jiuming; Chen, Yi; He, Jingjing; Gong, Tao; Tang, Fei; Wang, Xiaohao; Zhang, Ruiping; Huang, Lan; Zhang, Lianfeng; Lv, Haining; Ma, Shuanggang; Fu, Zhaodi; Chen, Xiaoguang; Yu, Shishan; Abliz, Zeper

    2013-03-01

    Whole-body molecular imaging is able to directly map spatial distribution of molecules and monitor its biotransformation in intact biological tissue sections. Imaging mass spectrometry (IMS), a label-free molecular imaging method, can be used to image multiple molecules in a single measurement with high specificity. Herein, a novel easy-to-implement, whole-body IMS method was developed with air flow-assisted ionization in a desorption electrospray ionization mode. The developed IMS method can effectively image molecules in a large whole-body section in open air without sample pretreatment, such as chemical labeling, section division, or matrix deposition. Moreover, the signal levels were improved, and the spatial assignment errors were eliminated; thus, high-quality whole-body images were obtained. With this novel IMS method, in situ mapping analysis of molecules was performed in adult rat sections with picomolar sensitivity under ambient conditions, and the dynamic information of molecule distribution and its biotransformation was provided to uncover molecular events at the whole-animal level. A global view of the differential distribution of an anticancer agent and its metabolites was simultaneously acquired in whole-body rat and model mouse bearing neuroglioma along the administration time. The obtained drug distribution provided rich information for identifying the targeted organs and predicting possible tumor spectrum, pharmacological activity, and potential toxicity of drug candidates.

  11. Enhanced one-photon double ionization of atoms and molecules in an environment of different species.

    PubMed

    Stumpf, V; Kryzhevoi, N V; Gokhberg, K; Cederbaum, L S

    2014-05-16

    The correlated nature of electronic states in atoms and molecules is manifested in the simultaneous emission of two electrons after absorption of a single photon close to the respective threshold. Numerous observations in atoms and small molecules demonstrate that the double ionization efficiency close to threshold is rather small. In this Letter we show that this efficiency can be dramatically enhanced in the environment. To be specific, we concentrate on the case where the species in question has one or several He atoms as neighbors. The enhancement is achieved by an indirect process, where a He atom of the environment absorbs a photon and the resulting He(+) cation is neutralized fast by a process known as electron transfer mediated decay, producing thereby doubly ionized species. The enhancement of the double ionization is demonstrated in detail for the example of the Mg · He cluster. We show that the double ionization cross section of Mg becomes 3 orders of magnitude larger than the respective cross section of the isolated Mg atom. The impact of more neighbors is discussed and the extension to other species and environments is addressed.

  12. Large Scale Nanoparticle Screening for Small Molecule Analysis in Laser Desorption Ionization Mass Spectrometry.

    PubMed

    Yagnik, Gargey B; Hansen, Rebecca L; Korte, Andrew R; Reichert, Malinda D; Vela, Javier; Lee, Young Jin

    2016-09-20

    Nanoparticles (NPs) have been suggested as efficient matrixes for small molecule profiling and imaging by laser-desorption ionization mass spectrometry (LDI-MS), but so far there has been no systematic study comparing different NPs in the analysis of various classes of small molecules. Here, we present a large scale screening of 13 NPs for the analysis of two dozen small metabolite molecules. Many NPs showed much higher LDI efficiency than organic matrixes in positive mode and some NPs showed comparable efficiencies for selected analytes in negative mode. Our results suggest that a thermally driven desorption process is a key factor for metal oxide NPs, but chemical interactions are also very important, especially for other NPs. The screening results provide a useful guideline for the selection of NPs in the LDI-MS analysis of small molecules. PMID:27573492

  13. Global molecular identification from graphs. Neutral and ionized main-group diatomic molecules.

    PubMed

    James, Bryan; Caviness, Ken; Geach, Jonathan; Walters, Chris; Hefferlin, Ray

    2002-01-01

    Diophantine equations and inequalities are presented for main-group closed-shell diatomic molecules. Specifying various bond types (covalent, dative, ionic, van der Waals) and multiplicities, it becomes possible to identify all possible molecules. While many of the identified species are probably unstable under normal conditions, they are interesting and present a challenge for computational or experimental analysis. Ionized molecules with net charges of -1, 1, and 2 are also identified. The analysis applies to molecules with atoms from periods 2 and 3 but can be generalized by substituting isovalent atoms. When closed-shell neutral diatomics are positioned in the chemical space (with axes enumerating the numbers of valence electrons of the free atoms), it is seen that they lie on a few parallel isoelectronic series.

  14. Properties of Hollow Molecules Probed by Single-Photon Double Ionization

    SciTech Connect

    Lablanquie, P.; Penent, F.; Palaudoux, J.; Selles, P.; Carniato, S.; Andric, L.; Bucar, K.; Zitnik, M.; Huttula, M.; Eland, J. H. D.; Shigemasa, E.; Soejima, K.; Hikosaka, Y.; Suzuki, I. H.; Nakano, M.; Ito, K.

    2011-02-11

    The formation of hollow molecules (with a completely empty K shell in one constituent atom) through single-photon core double ionization has been demonstrated using a sensitive magnetic bottle experimental technique combined with synchrotron radiation. Detailed properties are presented such as the spectroscopy, formation, and decay dynamics of the N{sub 2}{sup 2+} K{sup -2} main and satellite states and the strong chemical shifts of double K holes on an oxygen atom in CO, CO{sub 2}, and O{sub 2} molecules.

  15. Double ionization of single oriented water molecules by electron impact: Second-order Born description

    SciTech Connect

    Dal Cappello, C.; Champion, C.; Kada, I.; Mansouri, A.

    2011-06-15

    The double ionization of isolated water molecules fixed in space is investigated within a theoretical approach based on the second-order Born approximation. Electron angular distributions have been studied for specific kinematical conditions. The three usual mechanisms, the shake-off and the two two-step mechanisms, have been identified. A significant contribution of the two-step mechanism is clearly visible for some particular kinematics.

  16. Collisional radiative coarse-grain model for ionization in air

    NASA Astrophysics Data System (ADS)

    Panesi, Marco; Lani, Andrea

    2013-05-01

    We present a reduced kinetic mechanism for the modeling of the behavior of the electronic states of the atomic species in air mixtures. The model is built by lumping the electronically excited states of the atomic species and by performing Maxwell-Boltzmann averages of the rate constants describing the elementary kinetic processes of the individual states within each group. The necessary reaction rate coefficients are taken from the model compiled by Bultel et al. ["Collisional-radiative model in air for earth re-entry problems," Phys. Plasmas 13, 043502 (2006), 10.1063/1.2194827]. The reduced number of pseudo-states considered leads to a significant reduction of the computational cost, thus enabling the application of the state of the art collisional radiative models to bi-dimensional and three-dimensional problems. The internal states of the molecular species are assumed to be in equilibrium. The rotational energy mode is assumed to quickly equilibrate with the translational energy mode at the kinetic temperature of the heavy species as opposed to the electronic and the vibrational modes, assumed to be in Maxwell-Boltzmann equilibrium at a common temperature TV. In a first step we validate the model by using simple zero- and one-dimensional test cases for which the full kinetic mechanism can be run efficiently. Finally, the reduced kinetic model is used to analyze the strong non-equilibrium flow surrounding the FIRE II flight experiment during the early part of its re-entry trajectory. It is found that the reduced kinetic mechanism is capable of reproducing the ionizational non-equilibrium phenomena, responsible for the drastic reduction of the radiative heat loads on the space capsules during the re-entry phase.

  17. Intense electron-beam ionization physics in air

    NASA Astrophysics Data System (ADS)

    Strasburg, S.; Hinshelwood, D. D.; Schumer, J. W.; Mosher, D.; Ottinger, P. F.; Fernsler, R. F.; Slinker, S. P.

    2003-09-01

    In this paper we study, experimentally and theoretically, the interactions of an intense electron beam with an initially-neutral background gas. The Naval Research Laboratory's Gamble II generator [J. D. Shipman, Jr., IEEE Trans. Nucl. Sci. NS-18, 243 (1971)] was used to drive an annular 900 kV, 800 kA beam, whose effects on background air in the pressure range ˜0.01 to 10 Torr were studied. Experimental diagnostics included a sophisticated two-color interferometer for time-resolved measurements of the background electron density, B-dot monitoring of the global net current, and x-ray pinhole images of the beam location. Data obtained were compared to extensive simulations using three numerical models that incorporated complex beam physics, atomic processes, and the capability for simulating strongly-disturbed gases. Good simulation agreement with net current and electron density as a function of pressure was obtained using a scaled pressure. Simulated and experimental net current fractions (at peak beam current) for the 1-10 Torr collision-dominated transport regime were on the order of 10%, while ionization fractions after the beam pulse were 20% for 10 Torr, rising to nearly 100% at the lower pressure of 0.5 Torr. More advanced model development is underway to better understand the important physics of beam-gas interactions.

  18. Exploring the aqueous vertical ionization of organic molecules by molecular simulation and liquid microjet photoelectron spectroscopy.

    PubMed

    Tentscher, Peter R; Seidel, Robert; Winter, Bernd; Guerard, Jennifer J; Arey, J Samuel

    2015-01-01

    To study the influence of aqueous solvent on the electronic energy levels of dissolved organic molecules, we conducted liquid microjet photoelectron spectroscopy (PES) measurements of the aqueous vertical ionization energies (VIEaq) of aniline (7.49 eV), veratrole alcohol (7.68 eV), and imidazole (8.51 eV). We also reanalyzed previously reported experimental PES data for phenol, phenolate, thymidine, and protonated imidazolium cation. We then simulated PE spectra by means of QM/MM molecular dynamics and EOM-IP-CCSD calculations with effective fragment potentials, used to describe the aqueous vertical ionization energies for six molecules, including aniline, phenol, veratrole alcohol, imidazole, methoxybenzene, and dimethylsulfide. Experimental and computational data enable us to decompose the VIEaq into elementary processes. For neutral compounds, the shift in VIE upon solvation, ΔVIEaq, was found to range from ≈-0.5 to -0.91 eV. The ΔVIEaq was further explained in terms of the influence of deforming the gas phase solute into its solution phase conformation, the influence of solute hydrogen-bond donor and acceptor interactions with proximate solvent molecules, and the polarization of about 3000 outerlying solvent molecules. Among the neutral compounds, variability in ΔVIEaq appeared largely controlled by differences in solute-solvent hydrogen-bonding interactions. Detailed computational analysis of the flexible molecule veratrole alcohol reveals that the VIE is strongly dependent on molecular conformation in both gas and aqueous phases. Finally, aqueous reorganization energies of the oxidation half-cell ionization reaction were determined from experimental data or estimated from simulation for the six compounds aniline, phenol, phenolate, veratrole alcohol, dimethylsulfide, and methoxybenzene, revealing a surprising constancy of 2.06 to 2.35 eV. PMID:25516011

  19. Hand and shoe monitor using air ionization probes

    DOEpatents

    Fergus, Richard W.

    1981-01-01

    A hand and shoe radiation monitor is provided which includes a probe support body defining a plurality of cells, within each cell there being an ionization probe. The support body provides structural strength for protecting the ionization probes from force applied to the support body during a radiation monitoring event. There is also provided a fast response time amplifier circuit for the output from the ionization probes.

  20. First principles calculation of electron ionization mass spectra for selected organic drug molecules.

    PubMed

    Bauer, Christoph Alexander; Grimme, Stefan

    2014-11-21

    This study presents a showcase for the novel Quantum Chemistry Electron Ionization Mass Spectrometry (QCEIMS) method on five FDA-approved drugs. The method allows a first-principles electronic structure-based prediction of EI mass spectra in principle for any molecule. The systems in this case study are organic substances of nominal masses between 404 and 853 atomic mass units and cover a wide range of functional groups and organic molecular structure motifs. The results demonstrate the widespread applicability of the QCEIMS method for the unbiased computation of EI mass spectra even for larger molecules. Its strengths compared to standard (static) or database driven approaches in such cases are highlighted. Weak points regarding the required computation times or the approximate character of the employed QC methods are also discussed. We propose QCEIMS as a viable and robust way of predicting EI mass spectra for sizeable organic molecules relevant to medicinal and pharmaceutical chemistry.

  1. Charge symmetric dissociation of doubly ionized N{sub 2} and CO molecules

    SciTech Connect

    Pandey, A. Bapat, B.; Shamasundar, K. R.

    2014-01-21

    We report a comparative study of the features in dissociative double ionization by high energy electron impact of N{sub 2} and CO molecules. The ratio of cross-section of charge symmetric dissociative ionization to non-dissociative ionization (CSD-to-ND ratio) and the kinetic energy release (KER) spectra of dissociation are experimentally measured and carefully corrected for various ion transmission losses and detector inefficiencies. Given that the double ionization cross sections of these iso-electronic diatomics are very similar, the large difference in the CSD-to-ND ratios must be attributable to the differences in the evolution dynamics of the dications. To understand these differences, potential energy curves (PECs) of dications have been computed using multi-reference configuration interaction method. The Franck-Condon factors and tunneling life times of vibrational levels of dications have also been computed. While the KER spectrum of N{sub 2}{sup ++} can be readily explained by considering dissociation via repulsive states and tunneling of meta-stable states, indirect dissociation processes such as predissociation and autoionization have to be taken into account to understand the major features of the KER spectrum of CO{sup ++}. Direct and indirect processes identified on the basis of the PECs and experimental KER spectra also provide insights into the differences in the CSD-to-ND ratios.

  2. Charge symmetric dissociation of doubly ionized N2 and CO molecules.

    PubMed

    Pandey, A; Bapat, B; Shamasundar, K R

    2014-01-21

    We report a comparative study of the features in dissociative double ionization by high energy electron impact of N2 and CO molecules. The ratio of cross-section of charge symmetric dissociative ionization to non-dissociative ionization (CSD-to-ND ratio) and the kinetic energy release (KER) spectra of dissociation are experimentally measured and carefully corrected for various ion transmission losses and detector inefficiencies. Given that the double ionization cross sections of these iso-electronic diatomics are very similar, the large difference in the CSD-to-ND ratios must be attributable to the differences in the evolution dynamics of the dications. To understand these differences, potential energy curves (PECs) of dications have been computed using multi-reference configuration interaction method. The Franck-Condon factors and tunneling life times of vibrational levels of dications have also been computed. While the KER spectrum of N2 (++) can be readily explained by considering dissociation via repulsive states and tunneling of meta-stable states, indirect dissociation processes such as predissociation and autoionization have to be taken into account to understand the major features of the KER spectrum of CO(++). Direct and indirect processes identified on the basis of the PECs and experimental KER spectra also provide insights into the differences in the CSD-to-ND ratios. PMID:25669391

  3. LC-MS with electron ionization of cold molecules in supersonic molecular beams

    NASA Astrophysics Data System (ADS)

    Granot, Ori; Amirav, Aviv

    2005-06-01

    A new approach is described for the combination of electron ionization and LC-MS based on sample ionization as vibrationally cold molecules in a supersonic molecular beam (Cold EI). Cold EI of sample compounds in liquid solutions (methanol, acetonitrile, water, etc.) is achieved through spray formation, followed by soft thermal vaporization of the sample particles prior to their supersonic expansion and direct electron ionization of the sample compounds while they are contained in a supersonic molecular beam (SMB). Cold EI mass spectra were demonstrated to combine an enhanced molecular ion and improved mass spectral information (in comparison with standard EI), plus all the library searchable fragments. Cold EI enables the ionization of a broad range of compounds, including the full range of non-polar samples. Four orders of magnitude linear dynamic range is demonstrated and a detection limit of 2 pg was achieved for a 774 amu compound in single ion monitoring mode at m/z = 774. The method and apparatus are under continuous development and we feel that it can excel particularly in the analysis of unknown samples, while enabling fast LC-MS analysis through automated mass spectral deconvolution of coeluting LC peaks. In addition, the same MS system can also serve as an advanced GC-MS with supersonic molecular beams.

  4. Ionization and fragmentation of complex molecules studied with a density functional theory based approach

    NASA Astrophysics Data System (ADS)

    Kirchner, Tom

    2013-05-01

    Ion-impact induced ionization and fragmentation of complex molecules have important applications in many branches of science. If the molecule is H2O an obvious topic to address is the radiobiological relevance of these processes, e.g. in the context of hadron therapy, to name just one example. From a more fundamental physics viewpoint ion-molecule collision systems constitute interesting many-body systems, whose analysis poses challenges to both experimentalists and theorists. This talk will describe a theoretical approach to ion-molecule collisions, which is based on density functional theory to describe the nonperturbative electron dynamics. The basis generator method applied in the past successfully to ion-atom collisions is adapted to deal with the multi-center problem one faces when one considers molecular targets. Cross sections for single- and multiple-electron processes (capture and transfer to the continuum) are obtained directly from solving time-dependent Kohn-Sham-type orbital equations and using a Slater determinant based analysis. Fragmentation yields are predicted on the basis of a semi-phenomenological model which uses the calculated cross sections as input. Results will be presented for various ions impacting on water molecules in the energy range of 10-5000 keV/amu and compared with experimental data and previous theoretical calculations where available. First applications of the model to collisions involving CH4 molecules will also be discussed. This work has been supported by SHARCNET and NSERC Canada.

  5. Ionization-Enhanced Decomposition of 2,4,6-Trinitrotoluene (TNT) Molecules

    SciTech Connect

    Wang, Bin; Wright, David; Cliffel, David; HaglundJr., Richard F; Pantelides, Sokrates T.

    2011-01-01

    The unimolecular decomposition reaction of TNT can in principle be used to design ways to either detect or remove TNT from the environment. Here, we report the results of a density functional theory study of possible ways to lower the reaction barrier for this decomposition process by ionization, so that decomposition and/or detection can occur at room temperature. We find that ionizing TNT lowers the reaction barrier for the initial step of this decomposition. We further show that a similar effect can occur if a positive moiety is bound to the TNT molecule. The positive charge produces a pronounced electron redistribution and dipole formation in TNT with minimal charge transfer from TNT to the positive moiety.

  6. Correlation effects in strong-field ionization of heteronuclear diatomic molecules

    NASA Astrophysics Data System (ADS)

    Larsson, H. R.; Bauch, S.; Sørensen, L. K.; Bonitz, M.

    2016-01-01

    We develop a time-dependent theory to investigate electron dynamics and photoionization processes of diatomic molecules interacting with strong laser fields including electron-electron correlation effects. We combine the recently formulated time-dependent generalized-active-space configuration interaction theory [D. Hochstuhl and M. Bonitz, Phys. Rev. A 86, 053424 (2012), 10.1103/PhysRevA.86.053424; S. Bauch et al., Phys. Rev. A 90, 062508 (2014), 10.1103/PhysRevA.90.062508] with a prolate spheroidal basis set including localized orbitals and continuum states to describe the bound electrons and the outgoing photoelectron. As an example, we study the strong-field ionization of the two-center four-electron lithium hydride molecule in different intensity regimes. By using single-cycle pulses, two orientations of the asymmetric heteronuclear molecule are investigated: Li-H, with the electrical field pointing from H to Li, and the opposite case of H-Li. The preferred orientation for ionization is determined and we find a transition from H-Li, for low intensity, to Li-H, for high intensity. The influence of electron correlations is studied at different levels of approximation, and we find a significant change in the preferred orientation. For certain intensity regimes, even an interchange of the preferred configuration is observed, relative to the uncorrelated simulations. Further insight is provided by detailed comparisons of photoelectron angular distributions with and without correlation effects taken into account.

  7. Precise description of single and double ionization of hydrogen molecule in intense laser pulses

    NASA Astrophysics Data System (ADS)

    Vafaee, Mohsen; Sami, Firoozeh; Shokri, Babak; Buzari, Behnaz; Sabzyan, Hassan

    2012-07-01

    A new simulation box setup is introduced for the precise description of the wavepacket evolution of two electronic systems in intense laser pulses. In this box, the regions of the hydrogen molecule H2, and singly and doubly ionized species, H2^+ and H2^{+2}, are well discernible and their time-dependent populations are calculated at different laser field intensities. In addition, some new regions are introduced and characterized as quasi-double ionization and their time-dependencies on the laser field intensity are calculated and analyzed. The adopted simulation box setup is special in that it assures proper evaluation of the second ionization. In this study, the dynamics of the electrons and nuclei of the hydrogen molecule are separated based on the adiabatic approximation. The time-dependent Schrödinger and Newton equations are solved simultaneously for the electrons and the nuclei, respectively. Laser pulses of 390 nm wavelength at four different intensities (i.e., 1 × 1014, 5 × 1014, 1 × 1015, and 5 × 1015 W cm-2) are used in these simulations. Details of the central H2 region are also presented and discussed. This region is divided into four sub-regions related to the ionic state H+H- and covalent (natural) state HH. The effect of the motion of nuclei on the enhanced ionization is discussed. Finally, some different time-dependent properties are calculated, their dependencies on the intensity of the laser pulse are studied, and their correlations with the populations of different regions are analyzed.

  8. Above-threshold ionization of diatomic molecules by few-cycle laser pulses

    SciTech Connect

    Gazibegovic-Busuladzic, A.; Hasovic, E.; Busuladzic, M.; Milosevic, D. B.; Kelkensberg, F.; Siu, W. K.; Vrakking, M. J. J.; Lepine, F.; Sansone, G.; Nisoli, M.; Znakovskaya, I.; Kling, M. F.

    2011-10-15

    Above-threshold ionization of diatomic molecules by infrared carrier-envelope phase (CEP) stable few-cycle laser pulses is analyzed both experimentally and theoretically. The theoretical approach is based on the recently developed molecular improved strong-field approximation (ISFA), generalized to few-cycle pulses. Instead of using the first Born approximation, the rescattering matrix element in the ISFA is now calculated exactly. This modification leads to the appearance of characteristic minima in the differential cross section as a function of the scattering angle. Experimental angle-resolved photoelectron spectra of N{sub 2} and O{sub 2} molecules are obtained using the velocity map imaging technique. A relatively good agreement of experimental and simulated angle-resolved spectra, CEP-dependent asymmetry maps, and extracted electron-molecular ion elastic scattering differential cross sections is obtained.

  9. Multiphoton Ionization of Atoms and Molecules with Soft and Hard X-rays

    NASA Astrophysics Data System (ADS)

    Rolles, Daniel

    2015-05-01

    We have recently extended our previous investigations of the multiphoton ionization of heavy atoms, such as Kr and Xe, and of high-Z atom containing molecules from the soft into the hard X-ray range as well as into the XUV regime. Using the 100-nm focus environment at LCLS, we were able to reach peak intensities up to 1019W/cm2 at photon energies between 5 to 9 keV. This allows studying atomic and molecular ionization processes under unprecedented X-ray intensities and, in particular, under the identical conditions where typical coherent diffractive imaging experiments are performed. Our results are thus important benchmarks for calculating radiation damage effects in FEL-based X-ray imaging experiments. Using new micro-focusing capabilities at FLASH, we also extended our studies into the XUV range between 70 and 200 eV photon energy and observed significantly higher charge states than previously reported. I will present the results from our recent measurements at LCLS and FLASH and discuss the different multiphoton ionization mechanisms that play a role in the XUV, soft, and hard X-ray range.

  10. The electron-ion dynamics in ionization of lithium carbide molecule under femtosecond laser pulses

    NASA Astrophysics Data System (ADS)

    Zhang, Xiaoqin; Wang, Feng; Hong, Xuhai; Su, Wenyong; Gou, Bingcong; Chen, Huimin

    2016-08-01

    The electron-ion dynamics of the linear lithium carbide molecule under femtosecond laser pulses have been investigated in the framework of Ehrenfest molecular dynamics, in which valence electrons are treated quantum mechanically by time-dependent density functional theory (TDDFT) and ions are described classically. The on- and off-resonant multiphoton ionization processes have been induced by regulating laser frequency and laser intensity. The laser pulse with on-resonant frequency induces pronounced enhancement in electron ionization, bond length vibration, and energy absorption. Moreover, the coulomb explosion is preferred to occur in the on-resonant case, which is in qualitative agreement with previous theoretical investigations. The subtle relations between escaped electron number and absorbed photon number are well discussed with the increasing of laser intensity. Finally, the effect of self-interaction error is analyzed by comparing escaped electron number calculated with LDA and LDA-ADSIC. And the revTPSS-meta-GGA, a currently more accurate nonempirical exchange-correlation energy functional from a point of static density functional theory, is introduced to display its capability for the description of ionization process within nonlinear and the nonperturbative regime of isolated systems.

  11. 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.

  12. High-resolution field desorption/ionization fourier transform ion cyclotron resonance mass analysis of nonpolar molecules.

    PubMed

    Schaub, Tanner M; Hendrickson, Christopher L; Qian, Kuangnan; Quinn, John P; Marshall, Alan G

    2003-05-01

    We report the first field desorption ionization broadband high-resolution (m/Deltam(50%) approximately 65 000) mass spectra. We have interfaced a field ionization/field desorption source to a home-built 9.4-T FT-ICR mass spectrometer. The instrumental configuration employs convenient sample introduction (in-source liquid injection) and external ion accumulation. We demonstrate the utility of this configuration by generating high-resolution positive-ion mass spectra of C(60) and a midboiling crude oil distillate. The latter contains species not accessible by common soft-ionization methods, for example, low-voltage electron ionization, electrospray ionization, and matrix-assisted laser desorption/ionization. The present work demonstrates significant advantages of FI/FD FT-ICR MS for analysis of nonpolar molecules in complex mixtures.

  13. Characterization of a free air ionization chamber for low energy X-rays

    NASA Astrophysics Data System (ADS)

    Silva, N. F.; Xavier, M.; Vivolo, V.; Caldas, L. V. E.

    2016-07-01

    Free air ionization chambers are used by most primary metrology laboratories as primary standards of the quantities air kerma and exposure in X-ray beams. The free air ionization chamber for low energies of the Calibration Laboratory (LCI) of IPEN showed in a characterization test a problem in the set responsible for the variation of its sensitive volume. After a modification in the support of the micrometers used for the movement of the internal cylinder and the establishment of a new alignment system protocol, the tests were redone. The objective of this work was to present the results obtained in the new condition.

  14. Ionization Energy Measurements and Spectroscopy of the BeOBe Molecule

    NASA Astrophysics Data System (ADS)

    Merritt, J. M.; Bondybey, V. E.; Heaven, M. C.

    2009-06-01

    The Be_2O^+ cation was observed some fifty years ago in mass spectroscopic studies of vapors above heated beryllium oxide. From temperature and electron energy dependence of the ion abundance, Theard and Hildebrand (JCP 41, 3416 (1964)) deduced a value of -8±10 kcal/mole for the enthalpy of formation of neutral Be_2O in the gas phase. Such strong bonding of the second Be atom to BeO was, at the time, somewhat surprising given the initial view of a double bond in BeO, such that Be donates two electrons and the O atom would have a filled valence shell. More recent electronic structure calculations have shown that the bonding of BeO is intermediate between a single and double bond and thus can form a strong bond with a second Be atom. Calculations have also predicted that the ground electronic state of BeOBe is multi-reference in nature, thus accurate characterization of this molecule can be used to benchmark high-level multiconfigurational theoretical methods. The electronic structure of the BeOBe molecule has been investigated using laser induced fluorescence (LIF) and resonance enhanced multiphoton ionization (REMPI) tenchniques in the 27000-33000 cm^{-1} range. The BeOBe molecule has been stabilized in the gas phase using pulsed laser vaporization of Beryllium metal, and subsequent free jet expansion into vacuum. Vibrational progressions assigned to excitations of the symmetric and antisymmetric stretches in the excited state are observed and analyzed. Rotationally resolved spectra are found to exhibit nuclear spin statistics which confirm the ground electronic state of BeOBe has ^1Σ_g^+ symmetry. A BeO bond length of 1.399(3) Angstrom has been determined for the ground state. Photoionization efficiency curves were also recorded to determine an accurate ionization energy for BeOBe of 8.12(1) eV. Comparisons with electronic structure calculations will also be presented.

  15. Resonancelike enhancement in high-order above-threshold ionization of polyatomic molecules

    NASA Astrophysics Data System (ADS)

    Wang, C.; Okunishi, M.; Hao, X.; Ito, Y.; Chen, J.; Yang, Y.; Lucchese, R. R.; Zhang, M.; Yan, B.; Li, W. D.; Ding, D.; Ueda, K.

    2016-04-01

    We investigate the resonance-like enhancement (RLE) in high-order above-threshold ionization (ATI) spectra of the polyatomic molecules C2H4 and C2H6 . In the spectrum-intensity maps, strong and weak RLE areas emerge alternatively for both C2H4 and C2H6 but in different sequences. Theoretical calculations using the strong-field approximation reproduce the experimental observation and analysis shows that the different characteristics of the two molecules can be attributed to interference effects of molecular orbitals with different symmetries. For C2H4 , the RLE structures are attributed to C-C centers of the highest occupied molecular orbital (HOMO) orbital. For C2H6 , in contrast, the C-C centers of the HOMO and HOMO-1 orbitals do not contribute to the RLE due to destructive interference but the hydrogen centers of the bonding HOMO-1 orbital give rise to the multiple RLE regions. In addition, clear experimental evidence of the existence of two types of the RLE and their dependence on the parity of ground state is shown. Our result, which strongly supports the channel-closing mechanism of the RLE, for the first time reveals the important role of low-lying orbitals and the differing roles of different atomic centers in the high-order ATI spectrum of molecules.

  16. Resonant- and avalanche-ionization amplification of laser-induced plasma in air

    SciTech Connect

    Wu, Yue; Zhang, Zhili; Jiang, Naibo; Roy, Sukesh; Gord, James R.

    2014-10-14

    Amplification of laser-induced plasma in air is demonstrated utilizing resonant laser ionization and avalanche ionization. Molecular oxygen in air is ionized by a low-energy laser pulse employing (2 + 1) resonance-enhanced multi-photon ionization (REMPI) to generate seed electrons. Subsequent avalanche ionization of molecular oxygen and nitrogen significantly amplifies the laser-induced plasma. In this plasma-amplification effect, three-body attachments to molecular oxygen dominate the electron-generation and -loss processes, while either nitrogen or argon acts as the third body with low electron affinity. Contour maps of the electron density within the plasma obtained in O₂/N₂ and O₂/Ar gas mixtures are provided to show relative degrees of plasma amplification with respect to gas pressure and to verify that the seed electrons generated by O₂ 2 + 1 REMPI are selectively amplified by avalanche ionization of molecular nitrogen in a relatively low-pressure condition (≤100 Torr). Such plasma amplification occurring in air could be useful in aerospace applications at high altitude.

  17. Resonant- and avalanche-ionization amplification of laser-induced plasma in air

    NASA Astrophysics Data System (ADS)

    Wu, Yue; Zhang, Zhili; Jiang, Naibo; Roy, Sukesh; Gord, James R.

    2014-10-01

    Amplification of laser-induced plasma in air is demonstrated utilizing resonant laser ionization and avalanche ionization. Molecular oxygen in air is ionized by a low-energy laser pulse employing (2 + 1) resonance-enhanced multi-photon ionization (REMPI) to generate seed electrons. Subsequent avalanche ionization of molecular oxygen and nitrogen significantly amplifies the laser-induced plasma. In this plasma-amplification effect, three-body attachments to molecular oxygen dominate the electron-generation and -loss processes, while either nitrogen or argon acts as the third body with low electron affinity. Contour maps of the electron density within the plasma obtained in O2/N2 and O2/Ar gas mixtures are provided to show relative degrees of plasma amplification with respect to gas pressure and to verify that the seed electrons generated by O2 2 + 1 REMPI are selectively amplified by avalanche ionization of molecular nitrogen in a relatively low-pressure condition (≤100 Torr). Such plasma amplification occurring in air could be useful in aerospace applications at high altitude.

  18. Cobalt coated substrate for matrix-free analysis of small molecules by laser desorption/ionization mass spectrometry

    NASA Astrophysics Data System (ADS)

    Yalcin, Talat; Li, Liang

    2009-12-01

    Small molecule analysis is one of the most challenging issues in matrix-assisted laser desorption/ionization (MALDI) mass spectrometry. We have developed a cobalt coated substrate as a target for matrix-free analysis of small molecules in laser desorption/ionization mass spectrometry. Cobalt coating of 60-70 nm thickness has been characterized by scanning electron microscopy, energy dispersive X-ray analysis, X-ray diffraction, and laser induced breakdown spectroscopy. This target facilitates hundreds of samples to be spotted and analyzed without mixing any matrices, in a very short time. This can save a lot of time and money and can be a very practical approach for the analysis of small molecules by laser desorption/ionization mass spectrometry.

  19. [Mitogenic and mutagenic effects of ionized air on Allium fistulosum L].

    PubMed

    Trofimova, V A; P'ianzina, T A

    2005-09-01

    In the apical meristem of Allium fistulosum, the relationship between peroxide lipid oxidation, antioxidant activity, proliferative processes, the yield of chromosomal aberrations and duration the exposure to ionized air was studied. Under the influence of air oxygen ions, superoxide dismutase and catalase activities increased, proliferative processes were stimulated, and shifts occurred in the process of lipid peroxidation in cells of A. fistulosum. When these cells were treated with air oxygen for 40 min, hydrogen peroxide and iron sulfate (II) enhanced oxygen biostimulating effect via stimulation of antioxidant enzyme activity and inhibition of lipid peroxidation. Under these conditions, cell proliferation was intensified and the yield of chromosomal aberrations was reduced in A. fistulosum rootlets. When the time of seed treatment with ionized air was increased to 80 min, lipid peroxidation was activated, antioxidant enzyme activity was inhibited, and the yield of chromosomal aberration increased in seedlings. It was concluded that the biostimulating activity of ionized air was mediated by active oxygen species generated in the cell. The accumulation of TBA(thiobarbituric acid)-reactive products was shown to be related to a decrease in antioxidant enzyme activity and an increase in the yield of chromosomal aberrations. It is emphasized that the mutagenic effect of ionized air is associated with generating conditions that support Fenton reaction and OH-radical formation in the cell. PMID:16240634

  20. Interference effects in above-threshold ionization from diatomic molecules: Determining the internuclear separation

    SciTech Connect

    Hetzheim, H.; Figueira de Morisson Faria, C.; Becker, W.

    2007-08-15

    We calculate angle-resolved above-threshold ionization spectra for diatomic molecules in linearly polarized laser fields, employing the strong-field approximation. The interference structure resulting from the individual contributions of the different scattering scenarios is discussed in detail, with respect to the dependence on the internuclear distance and molecular orientation. We show that, in general, the contributions from the processes in which the electron is freed at one center and rescatters off the other obscure the interference maxima and minima obtained from single-center processes. However, around the boundary of the energy regions for which rescattering has a classical counterpart, such processes play a negligible role and very clear interference patterns are observed. In such energy regions, one is able to infer the internuclear distance from the energy difference between adjacent interference minima.

  1. Selective ionization/dissociation of oriented N2O molecules by asymmetric fs laser field.

    PubMed

    Kotsina, N; Kaziannis, S; Danakas, S; Kosmidis, C

    2013-09-14

    We report on the selective ionization of oriented nitrous oxide (N2O) molecules in gas phase by the use of an intense asymmetric two-color ω/2ω 40 fs laser field. By means of a time-of-flight mass spectrometer the induced N2O mass spectra have been recorded as a function of the relative phase of the two-color laser fields. It is found that the applied method facilitates the distinction of different dissociation channels that result in fragments with the same mass and kinetic energy. Thus, the potential of the employed technique for phase control of the molecular excitation for the case of N2O is explored.

  2. Attosecond probing of state-resolved ionization and superpositions of atoms and molecules

    NASA Astrophysics Data System (ADS)

    Leone, Stephen

    2016-05-01

    Isolated attosecond pulses in the extreme ultraviolet are used to probe strong field ionization and to initiate electronic and vibrational superpositions in atoms and small molecules. Few-cycle 800 nm pulses produce strong-field ionization of Xe atoms, and the attosecond probe is used to measure the risetimes of the two spin orbit states of the ion on the 4d inner shell transitions to the 5p vacancies in the valence shell. Step-like features in the risetimes due to the subcycles of the 800 nm pulse are observed and compared with theory to elucidate the instantaneous and effective hole dynamics. Isolated attosecond pulses create massive superpositions of electronic states in Ar and nitrogen as well as vibrational superpositions among electronic states in nitrogen. An 800 nm pulse manipulates the superpositions, and specific subcycle interferences, level shifting, and quantum beats are imprinted onto the attosecond pulse as a function of time delay. Detailed outcomes are compared to theory for measurements of time-dynamic superpositions by attosecond transient absorption. Supported by DOE, NSF, ARO, AFOSR, and DARPA.

  3. 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

  4. Effect of long-term ionized air treatment on patients with bronchial asthma.

    PubMed

    Jones, D P; O'Connor, S A; Collins, J V; Watson, B W

    1976-08-01

    Seven patients with bronchial asthma requiring continuous medication were subjected to eight weeks of nocturnal exposure to negatively ionized air, and their progress was followed using objective tests of lung function and clinical assessment. During exposure, four patients showed significant increases in morning PEFR, which in two of these patients was not sustained when exposure ceased. In two patients the observed increase in PEFR was accompanied by subjective improvement. From the results of all our assessments we conclude that, although this treatment may lead to an improvement in some patients with asthma, further objective studies are required to determine the value of negatively ionized air in the routine management of asthma.

  5. The dissociative single and double ionization of some simple molecules by fast ions and VUV photons

    NASA Astrophysics Data System (ADS)

    Browne, Clive Ronald Harold

    The partial cross sections for the production of energetic fragment protons/deuterons in the dissociative photoionization of HCl/DCl and H2S/D2 S have been determined using vacuum ultraviolet (VUV) photons in the 20-50eV photon energy range. Thresholds in the gross structure of the partial photoionization. cross sections were visible and these values were found to agree well with previous experimental and theoretical data corresponding to Franck-Condon excitations. The kinetic energy spectra of the fragment protons/deuterons produced in the dissociative single and double photoionization of HCl/DCl and H 2S/D2S by 20-50eV photons have been obtained for the first time. The nature of the fragment ions shown in the energy spectra confirm the important role played by indirect fragmentation mechanisms, especially in the double ionization processes. Complementary mass and kinetic energy spectra of the molecular fragment ions formed in the dissociative ionization of the CH4, C2 H2, C2H4, C2H6, and C3H8 group of hydrocarbons have been measured using fast (3-30keV) H+ and He+ ions. The observed differences, between projectiles, in the mass and energy spectra indicate that in contrast to H+, fragmentation of the molecules by He + ions is not governed by the Born approximation. An investigation has also been carried out into the energy distribution of the fragment ion-pairs produced in the dissociative double ionization of H2, D2, H2O and N2 by fast (3-30keV) ion impact. The kinetic energy spectra show ample evidence of low energy (2-7eV) ions and ion-pairs, in agreement with previous reports, supporting the suggestion that they are formed through two-electron excited autoionizing states. The energy distributions of N+N+ ion-pairs produced from the dissociative ionization of N2 by He+ ions shows considerable structure and some interesting contrasts with those produced by H+ ions.

  6. Intense-field ionization of atoms and molecules: Spatially resolved ion detection and ultrashort optical vortices

    NASA Astrophysics Data System (ADS)

    Strohaber, James

    The interaction of light and matter has for many years provided a venue in which scientists have been able to increase their understanding of fundamental quantum mechanics and electromagnetism. The advent of the laser in the early sixties significantly changed the way in which experiments were performed. These coherent sources of radiation played a pivotal role in the investigations of new phenomenon such as multiphoton ionization. As time progressed many significant advances have been made in laser technology. For instance, the development of mode-locking techniques such as Q-switching and the nonlinear Kerr effect have made pulsed lasers possible (now down to ˜ 5 fs), the discovery of Chirped-Pulse-Amplification allowed for these ultrashort pulses to be amplified up to Joules in energy per pulse. As a result of these new advances in laser technology, new and exciting physics have been illuminated. When ultrashort intense laser fields interact with matter, one possible outcome is the ionization of the target into its constituents (atoms, molecules, electrons or photons). Because the constituents are usually ions which may have different masses and charges, time-of-flight (TOF) techniques are often employed in the analysis of the ionization yields. In these experiments, the usual quantity of physical interest is the ionization probability as a function of a well known intensity. However, in reality the impinging laser radiation possesses a distribution of intensities. To further add to this annoyance, it is difficult for a TOF spectrometer to distinguish between ions created at different intensities and the usual course of action is to integrate ions from over the entire focal volume. The inevitable result of this so-called spatial averaging is to limit information about the underlying physical process. Additionally, coherent sources of radiation have captured the attention of researchers whose main interests are in spatially modulating the phase and amplitude of

  7. Relation between molecule ionization energy, film thickness and morphology of two indandione derivatives thin films

    NASA Astrophysics Data System (ADS)

    Grzibovskis, Raitis; Vembris, Aivars; Pudzs, Kaspars

    2016-08-01

    Nowadays most organic devices consist of thin (below 100 nm) layers. Information about the morphology and energy levels of thin films at such thickness is essential for the high efficiency devices. In this work we have investigated thin films of 2-(4-[N,N-dimethylamino]-benzylidene)-indene-1,3-dione (DMABI) and 2-(4-(bis(2-(trityloxy)ethyl)amino)benzylidene)-2H-indene-1,3-dione (DMABI-6Ph). DMABI-6Ph is the same DMABI molecule with attached bulky groups which assist formation of amorphous films from solutions. Polycrystalline structure was obtained for the DMABI thin films prepared by thermal evaporation in vacuum and amorphous structure for the DMABI-6Ph films prepared by spin-coating method. Images taken by SEM showed separate crystals or islands at the thickness of the samples below 100 nm. The ionization energy of the studied compounds was determined using photoemission yield spectroscopy. A vacuum level shift of 0.40 eV was observed when ITO electrode was covered with the thin film of the organic compound. Despite of the same active part of the investigated molecules the ITO/DMABI interface is blocking electrons while ITO/DMABI-6Ph interface is blocking holes.

  8. High Energy Proton Ejection from Hydrocarbon Molecules Driven by Highly Efficient Field Ionization

    NASA Astrophysics Data System (ADS)

    Roither, S.; Xie, X.; Kartashov, D.; Zhang, L.; Schöffler, M.; Xu, H.; Iwasaki, A.; Okino, T.; Yamanouchi, K.; Baltuška, A.; Kitzler, M.

    We report on the ejection of protons with surprisingly high kinetic energies up to 60 eV from a series of polyatomic hydrocarbon molecules exposed to Titanium-Sapphire laser pulses with moderate laser peak intensities of a few 1014 W/cm2. Using multi-particle coincidence imaging we are able to decompose the observed proton energy spectra into the contributions of individual fragmentation channels. It is shown that the molecules can completely fragment into bare atomic ions already at relatively low peak intensities, and that the protons are ejected in a concerted Coulomb explosion from unexpectedly high charge states. We propose that a thus far undescribed process, namely that enhanced ionization (EI) taking place at all C-H bonds in parallel, is responsible for the high charge states and high proton energies. The proposition is successfully tested by using (stretched) few-cycle pulses with a bandwidth limited duration as short as 4.3 fs, for which the C-H nuclear motion is too slow to reach the critical internuclear distance for EI.

  9. PTRAC File Utilization for Calculation of Free-Air Ionization Chamber Correction Factors by MCNPX

    NASA Astrophysics Data System (ADS)

    Šolc, Jaroslav; Sochor, Vladimír

    2014-06-01

    A free-air ionization chamber is used as a standard of photon air-kerma. Several correction factors are applied to the air-kerma value. Correction factors for electron loss (kloss) and for additional ionization current caused by photon scatter (ksc), photon fluorescence (kfl), photon transmission through diaphragm edge (kdtr), and photon scatter from the surface of the diaphragm aperture (kdsc) were determined by the MCNPX code utilizing information stored in Particle Track (PTRAC) output files. Individual steps of the procedure are described and the calculated values of the correction factors are presented. The values are in agreement with the correction factors published in a literature for similar free-air chambers.

  10. Nonadiabatic tunnel ionization of current-carrying orbitals of prealigned linear molecules in strong circularly polarized laser fields

    NASA Astrophysics Data System (ADS)

    Liu, Kunlong; Barth, Ingo

    2016-10-01

    We derive the analytical formula of the ratio of the ionization rates of degenerate valence π± orbitals of prealigned linear molecules in strong circularly polarized (CP) laser fields. Interestingly, our theory shows that the ionization ratio for molecular orbitals with opposite azimuthal quantum numbers ±|m | (e.g., π±) is identical to that for atomic orbitals with the same ±|m | (e.g., p±). In general, the electron counter-rotating to the CP laser field tunnels more easily, not only for atoms but also for linear molecules. Our theoretical predictions are then verified by numerically solving the three-dimensional time-dependent Schrödinger equation for the ionization of the prealigned nitric oxide (NO) molecule in strong CP laser fields. Due to the spin-orbital coupling in the electronic ground state of NO and the sensitivity of ionization to the sense of electron rotation, the ionization of NO in CP fields can produce spin-polarized photoelectrons with high controllability of spin polarization up to 100 % .

  11. Precision measurements of ionization and dissociation energies by extrapolation of Rydberg series: from H2 to larger molecules.

    PubMed

    Sprecher, D; Beyer, M; Merkt, F

    2013-01-01

    Recent experiments are reviewed which have led to the determination of the ionization and dissociation energies of molecular hydrogen with a precision of 0.0007 cm(-)1 (8 mJ/mol or 20 MHz) using a procedure based on high-resolution spectroscopic measurements of high Rydberg states and the extrapolation of the Rydberg series to the ionization thresholds. Molecular hydrogen, with only two protons and two electrons, is the simplest molecule with which all aspects of a chemical bond, including electron correlation effects, can be studied. Highly precise values of its ionization and dissociation energies provide stringent tests of the precision of molecular quantum mechanics and of quantum-electrodynamics calculations in molecules. The comparison of experimental and theoretical values for these quantities enable one to quantify the contributions to a chemical bond that are neglected when making the Born-Oppenheimer approximation, i.e. adiabatic, nonadiabatic, relativistic, and radiative corrections. Ionization energies of a broad range of molecules can now be determined experimentally with high accuracy (i.e. about 0.01 cm(-1)). Calculations at similar accuracies are extremely challenging for systems containing more than two electrons. The combination of precision measurements of molecular ionization energies with highly accurateab initio calculations has the potential to provide, in future, fully reliable sets of thermochemical quantities for gas-phase reactions. PMID:23967701

  12. Strong-field approximation for ionization of a diatomic molecule by a strong laser field. III. High-order above-threshold ionization by an elliptically polarized field

    SciTech Connect

    Busuladzic, M.; Gazibegovic-Busuladzic, A.; Milosevic, D. B.

    2009-07-15

    We investigate high-order above-threshold ionization (HATI) of diatomic molecules having different symmetries by an elliptically polarized laser field using the modified molecular strong-field approximation. The yields of high-energy electrons contributing to the plateau region of the photoelectron spectra strongly depend on the employed ellipticity. This is more pronounced if the major axis of the polarization ellipse is parallel or perpendicular to the molecular axis and at the end of the high-energy plateau. For the O{sub 2} molecule (characterized by {pi}{sub g} symmetry) the maximum yield is observed for some value of the ellipticity {epsilon} different from zero. On the other hand, in the same circumstances, the N{sub 2} molecule ({sigma}{sub g}) behaves as an atom, i.e., the yield is maximum for {epsilon}=0. These characteristics of the photoelectron spectra remain valid in a wide region of the molecular orientations and laser peak intensities. The symmetry properties of the molecular HATI spectra are considered in detail: by changing the molecular orientation one or other type of the symmetry emerges or disappears. Presenting differential ionization spectra in the ionized electron energy-emission angle plane we have observed similar interference effects as in the HATI spectra governed by a linearly polarized field.

  13. Near infrared (NIR) strong field ionization and imaging of C₆₀ sputtered molecules: overcoming matrix effects and improving sensitivity.

    PubMed

    Kucher, Andrew; Jackson, Lauren M; Lerach, Jordan O; Bloom, A N; Popczun, N J; Wucher, Andreas; Winograd, Nicholas

    2014-09-01

    Strong field ionization (SFI) was applied for the secondary neutral mass spectrometry (SNMS) of patterned rubrene films, mouse brain sections, and Botryococcus braunii algal cell colonies. Molecular ions of rubrene, cholesterol, C31 diene/triene, and three wax monoesters were detected, representing some of the largest organic molecules ever ionized intact by a laser post-ionization experiment. In rubrene, the SFI SNMS molecular ion signal was ~4 times higher than in the corresponding secondary-ion mass spectroscopy (SIMS) analysis. In the biological samples, the achieved signal improvements varied among molecules and sampling locations, with SFI SNMS, in some cases, revealing analytes made completely undetectable by the influence of matrix effects in SIMS. PMID:25109240

  14. Theoretical and experimental quantification of doubly and singly differential cross sections for electron-induced ionization of isolated tetrahydrofuran molecules

    DOE PAGES

    Champion, Christophe; Quinto, Michele A.; Bug, Marion U.; Baek, Woon Y.; Weck, Philippe F.

    2014-07-29

    Electron-induced ionization of the commonly used surrogate of the DNA sugar-phosphate backbone, namely, the tetrahydrofuran molecule, is here theoretically described within the 1st Born approximation by means of quantum-mechanical approach. Comparisons between theory and recent experiments are reported in terms of doubly and singly differential cross sections.

  15. Theoretical and experimental quantification of doubly and singly differential cross sections for electron-induced ionization of isolated tetrahydrofuran molecules

    SciTech Connect

    Champion, Christophe; Quinto, Michele A.; Bug, Marion U.; Baek, Woon Y.; Weck, Philippe F.

    2014-07-29

    Electron-induced ionization of the commonly used surrogate of the DNA sugar-phosphate backbone, namely, the tetrahydrofuran molecule, is here theoretically described within the 1st Born approximation by means of quantum-mechanical approach. Comparisons between theory and recent experiments are reported in terms of doubly and singly differential cross sections.

  16. Ionization of one- and three-dimensionally-oriented asymmetric-top molecules by intense circularly polarized femtosecond laser pulses

    SciTech Connect

    Hansen, Jonas L.; Holmegaard, Lotte; Kalhoej, Line; Kragh, Sofie Louise; Stapelfeldt, Henrik; Filsinger, Frank; Meijer, Gerard; Kuepper, Jochen; Dimitrovski, Darko; Abu-samha, Mahmoud; Martiny, Christian Per Juul; Madsen, Lars Bojer

    2011-02-15

    We present a combined experimental and theoretical study on strong-field ionization of a three-dimensionally-oriented asymmetric top molecule, benzonitrile (C{sub 7}H{sub 5}N), by circularly polarized, nonresonant femtosecond laser pulses. Prior to the interaction with the strong field, the molecules are quantum-state selected using a deflector and three-dimensionally (3D) aligned and oriented adiabatically using an elliptically polarized laser pulse in combination with a static electric field. A characteristic splitting in the molecular frame photoelectron momentum distribution reveals the position of the nodal planes of the molecular orbitals from which ionization occurs. The experimental results are supported by a theoretical tunneling model that includes and quantifies the splitting in the momentum distribution. The focus of the present article is to understand strong-field ionization from 3D-oriented asymmetric top molecules, in particular the suppression of electron emission in nodal planes of molecular orbitals. In the preceding article [Dimitrovski et al., Phys. Rev. A 83, 023405 (2011)] the focus is to understand the strong-field ionization of one-dimensionally-oriented polar molecules, in particular asymmetries in the emission direction of the photoelectrons.

  17. Theoretical and experimental quantification of doubly and singly differential cross sections for electron-induced ionization of isolated tetrahydrofuran molecules

    NASA Astrophysics Data System (ADS)

    Champion, Christophe; Quinto, Michele A.; Bug, Marion U.; Baek, Woon Y.; Weck, Philippe F.

    2014-07-01

    Electron-induced ionization of the tetrahydrofuran molecule, the commonly used surrogate of the DNA sugar-phosphate backbone, is theoretically described in this study within the 1st Born approximation. Comparisons between theory and recent experiments are reported in terms of doubly and singly differential cross sections.

  18. Universal imaging: Dissociative ionization of polyatomic molecules, chemical dynamics beamline 9.0.2

    SciTech Connect

    Ahmed, M.; Chen, D.; Suits, A.G.

    1997-04-01

    A third endstation was recently added to the Chemical Dynamics beamline, designed to exploit the high flux broadband undulator light for a range of studies of reactive scattering, photochemistry and photoionization processes using time-of-flight mass spectroscopy coupled with position-sensitive detection. Two molecular beam sources are fixed at right angles, with the undulator light, or laser beams, intersecting the molecular beams at 45{degrees}. To date, beamline experiments have included a study of dissociative photoionization of a variety of molecules including N{sub 2}O and SF{sub 6}. In this mode, a single molecular beam source is used, with the tunable undulator light inducing, in SF{sub 6} for example, the process SF{sub 6} {r_arrow} SF{sub 6}{sup +} + e{sup {minus}} {r_arrow} SF{sub 5}{sup +} + F + e{sup {minus}}. The SF{sub 5}{sup +} ions are accelerated up the flight tube, mass selected and detected as a function of position on a phosphor screen viewed by a CCD camera. The position directly reveals the recoil speed (or translational energy release) and angular distribution for the dissociative ionization process. Furthermore, this measurement is obtained for all recoil speeds and angles simultaneously. Such detailed angular information has not previously been obtained for dissociative ionization processes; typically ion time-of-flight profiles are deconvoluted to yield rough insight into the angular distributions. The recorded image is actually a 2-dimensional projection of the nascent 3-dimensional velocity distribution, but established tomographic techniques enable the authors to reconstruct the 3-D distribution.

  19. Dressed-bound-state molecular strong-field approximation: Application to above-threshold ionization of heteronuclear diatomic molecules

    SciTech Connect

    Hasovic, E.; Busuladzic, M.; Becker, W.; Milosevic, D. B.

    2011-12-15

    The molecular strong-field approximation (MSFA), which includes dressing of the molecular bound state, is introduced and applied to above-threshold ionization of heteronuclear diatomic molecules. Expressions for the laser-induced molecular dipole and polarizability as functions of the laser parameters (intensity and frequency) and molecular parameters [molecular orientation, dipole, and parallel and perpendicular polarizabilities of the highest occupied molecular orbital (HOMO)] are presented. Our previous MSFA theory, which incorporates the rescattering effects, is generalized from homonuclear to heteronuclear diatomic molecules. Angle- and energy-resolved high-order above-threshold ionization spectra of oriented heteronuclear diatomic molecules, exemplified by the carbon monoxide (CO) molecule, exhibit pronounced minima, which can be related to the shape of their HOMO-electron-density distribution. For the CO molecule we have found an analytical condition for the positions of these minima. We have also shown that the effect of the dressing of the HOMO is twofold: (i) the laser-induced Stark shift decreases the ionization yield and (ii) the laser-induced time-dependent dipole and polarizability change the oscillatory structure of the spectra.

  20. Air-kerma determination using a variable-volume cavity ionization chamber standard.

    PubMed

    Burns, D T; Kessler, C; Roger, P

    2007-12-01

    A graphite-walled cavity ionization chamber of modular design and variable volume has been used to determine the air-kerma rate in the reference 60Co field at the BIPM. The chamber can be configured in five sizes. High-accuracy mechanical measurements of the volume of the air cavity were made for each configuration using a co-ordinate measuring machine. Ionization current measurements were made for each configuration and corrected for the effects of ion recombination and diffusion, stem scatter and chamber orientation. Monte Carlo calculations of cavity dose were made to evaluate the correction factors kwall and kan. A reproducibility of the ionization current per mass of 1.5 parts in 10(4) was achieved on the repeated assembly of each configuration. The results show an air-kerma rate determination that increases with volume, the total change being around 8 parts in 10(4). When analysed differentially, the air-kerma rate relative to the BIPM standard is Kdiff/KBIPM = 1.0026(6). A detailed uncertainty budget is presented. Possible reasons for the observed behaviour are discussed that might have consequences for all existing standards for air-kerma.

  1. Effect of ionizing radiation on moist air systems

    SciTech Connect

    Reed, D.T.; Van Konynenburg, R.A.

    1987-12-31

    The radiation chemistry of nitrogen/oxygen/water systems is reviewed. General radiolytic effects in dry nitrogen/oxygen systems are relatively well characterized. Irradiation results in the formation of steady state concentrations of ozone, nitrous oxide and nitrogen dioxide. In closed systems, the concentration observed depends on the total dose, temperature and initial gas composition. Only three studies have been published that focus on the radiation chemistry of nitrogen/oxygen/water homogeneous gas systems. Mixed phase work that is relevant to the gaseous system is also summarized. The presence of water vapor results in the formation of nitric acid and significantly changes the chemistry observed in dry air systems. Mechanistic evidence from the studies reviewed are summarized and discussed in relation to characterizing the gas phase during the containment period of a repository in tuff.

  2. Two-photon double-ionization of the H2 molecule: effects of pulse duration

    NASA Astrophysics Data System (ADS)

    Guan, Xiaoxu; Bartschat, Klaus; Koesterke, Lars; Schneider, Barry

    2013-05-01

    In previous work, we solved the time-dependent Schrödinger equation to calculate the two-photon double ionization of the hydrogen molecule induced by non-sequential absorption of photons with a central energy of 30 eV in a short laser pulse lasting for about 1.6 femtoseconds. At the equilibrium internuclear separation, however, several doubly excited 1Σg , u states lie about 30 eV above the ground X1Σg state. There is significant disagreement among various results published to date on this problem already for the angle-integrated cross section, and hence for the angular distribution as well. In the present work we address and clarify the fundamental role of those doubly excited states, which are accessible through photon absorption, on the two-photon breakup process. This can only be achieved by allowing for much longer laser pulses. Work supported by the NSF under PHY-1068140 and the XSEDE allocation PHY-090031.

  3. Double ionization of the water molecule: Influence of the target orientation on the secondary-electron angular distributions

    SciTech Connect

    Oubaziz, D.; Aouchiche, H.; Champion, C.

    2011-01-15

    Fivefold differential cross sections for electron-induced double ionization of isolated oriented water molecules are reported. The theoretical investigation is performed within the first Born approximation by describing the initial molecular state by means of single-center wave functions. The contributions of each final state to the double-ionization process, i.e., with target electrons ejected from similar and/or different molecular subshells, are studied and compared in terms of shape and magnitude. Furthermore, for the particular target orientations investigated, we identify clearly the signature of the main scenarios involved in (e,3e) reactions, namely, the shake-off and the two-step 1 mechanisms.

  4. Angle-Resolved High-Order Above-Threshold Ionization of a Molecule: Sensitive Tool for Molecular Characterization

    SciTech Connect

    Busuladzic, M.; Gazibegovic-Busuladzic, A.; Milosevic, D. B.; Becker, W.

    2008-05-23

    The strong-field approximation for ionization of diatomic molecules by an intense laser field is generalized to include rescattering of the ionized electron off the various centers of its molecular parent ion. The resulting spectrum and its interference structure strongly depend on the symmetry of the ground state molecular orbital. For N{sub 2}, if the laser polarization is perpendicular to the molecular axis, we observe a distinct minimum in the emission spectrum, which survives focal averaging and allows determination of, e.g., the internuclear separation. In contrast, for O{sub 2}, rescattering is absent in the same situation.

  5. Ignition of hydrocarbon-air supersonic flow by volumetric ionization

    NASA Astrophysics Data System (ADS)

    Goldfeld, Marat A.; Pozdnyakov, George A.

    2015-11-01

    The paper describes the results of the electron-beam initiation of the combustion in the mixtures of hydrogen, natural gas or kerosene vapors with air. Electron beam characteristics were studied in closed volume with immobile gas. The researches included definition of an integrated current of an electronic beam, distribution of a current density and an estimation of average energy of electrons. Possibility of fuel mixtures ignition by means of this approach in the combustor at high velocity at the entrance was demonstrated. Experiments were carried out at Mach numbers of 4 and 5. Process of ignition and combustion under electron beam action was researched. It was revealed that ignition of mixture occurs after completion of electron gun operation. Data obtained have confirmed effectiveness of electron beam application for ignition of hydrogen and natural gas. The numerical simulation of the combustion of mixture in channel was carried out by means of ANSYS CFD 12.0 instrumentation on the basis of Reynolds averaged Navier-Stokes equation using SST/k-ω turbulence model. For combustion modeling, a detailed kinetic scheme with 38 reactions of 8 species was implemented taking into account finite rate chemistry. Computations have shown that the developed model allow to predict ignition of a mixture and flame propagation even at low flow temperatures.

  6. Probing Orbital Symmetry of Molecules Via Alignment-Dependent Ionization Probability and High-Order Harmonic Generation by Intense Lasers

    NASA Astrophysics Data System (ADS)

    Zhao, Song-Feng; Zhou, Xiao-Xin; Lin, C. D.

    It is shown that measurement of alignment-dependent ionization probability and high-order harmonic generation (HHG) of molecules in an intense laser field can be used to probe the orbital symmetry of molecules. In this review, recent progress of molecular tunneling ionization (MO-ADK) model of Tong et al. [Phys. Rev. A 66, 033402 (2002)] is first reviewed. In particular, an efficient method to obtain wavefunctions of linear molecules in the asymptotic region was developed by solving the time-independent Schrödinger equation with B-spline functions, and molecular potential energy surfaces were constructed based on the density functional theory. The accurate wavefunctions are used to extract improved structure parameters in the MO-ADK model. The loss of accuracy of the MO-ADK model in the low intensity multiphoton ionization regime is also addressed by comparing with the molecular Perelomov-Popov-Terent'ev (MO-PPT) model, the single-active-electron time-dependent Schrödinger equation (SAE-TDSE) method, and the experimental data. Finally, how the orbital symmetry affects the HHG of molecules within the strong-field approximation (SFA) was reviewed.

  7. Ionizing air affects influenza virus infectivity and prevents airborne-transmission.

    PubMed

    Hagbom, Marie; Nordgren, Johan; Nybom, Rolf; Hedlund, Kjell-Olof; Wigzell, Hans; Svensson, Lennart

    2015-01-01

    By the use of a modified ionizer device we describe effective prevention of airborne transmitted influenza A (strain Panama 99) virus infection between animals and inactivation of virus (>97%). Active ionizer prevented 100% (4/4) of guinea pigs from infection. Moreover, the device effectively captured airborne transmitted calicivirus, rotavirus and influenza virus, with recovery rates up to 21% after 40 min in a 19 m(3) room. The ionizer generates negative ions, rendering airborne particles/aerosol droplets negatively charged and electrostatically attracts them to a positively charged collector plate. Trapped viruses are then identified by reverse transcription quantitative real-time PCR. The device enables unique possibilities for rapid and simple removal of virus from air and offers possibilities to simultaneously identify and prevent airborne transmission of viruses. PMID:26101102

  8. Ionizing air affects influenza virus infectivity and prevents airborne-transmission

    PubMed Central

    Hagbom, Marie; Nordgren, Johan; Nybom, Rolf; Hedlund, Kjell-Olof; Wigzell, Hans; Svensson, Lennart

    2015-01-01

    By the use of a modified ionizer device we describe effective prevention of airborne transmitted influenza A (strain Panama 99) virus infection between animals and inactivation of virus (>97%). Active ionizer prevented 100% (4/4) of guinea pigs from infection. Moreover, the device effectively captured airborne transmitted calicivirus, rotavirus and influenza virus, with recovery rates up to 21% after 40 min in a 19 m3 room. The ionizer generates negative ions, rendering airborne particles/aerosol droplets negatively charged and electrostatically attracts them to a positively charged collector plate. Trapped viruses are then identified by reverse transcription quantitative real-time PCR. The device enables unique possibilities for rapid and simple removal of virus from air and offers possibilities to simultaneously identify and prevent airborne transmission of viruses. PMID:26101102

  9. Measurement of nonlinear refractive index and ionization rates in air using a wavefront sensor.

    PubMed

    Schwarz, Jens; Rambo, Patrick; Kimmel, Mark; Atherton, Briggs

    2012-04-01

    A wavefront sensor has been used to measure the Kerr nonlinear focal shift of a high intensity ultrashort pulse beam in a focusing beam geometry while accounting for the effects of plasma-defocusing. It is shown that plasma-defocusing plays a major role in the nonlinear focusing dynamics and that measurements of Kerr nonlinearity and ionization are coupled. Furthermore, this coupled effect leads to a novel way that measures the laser ionization rates in air under atmospheric conditions as well as Kerr nonlinearity. The measured nonlinear index n₂ compares well with values found in the literature and the measured ionization rates could be successfully benchmarked to the model developed by Perelomov, Popov, and Terentev (PPT model) [Sov. Phys. JETP 50, 1393 (1966)].

  10. Design, simulation, and fabrication of a MEMS-based air amplifier for electrospray ionization

    NASA Astrophysics Data System (ADS)

    Jurčíček, Petr; Zou, Helin; Gao, Shuai

    2013-04-01

    Recent developments in electrospray ionization mass spectrometry (ESI-MS) show that air amplifiers can be utilized to significantly enhance droplet desolvation and to focus gas-phase ions when provided between an electrospray (ES) source and the mass spectrometer (MS). However, these devices are bulky and expensive, which may be a factor prohibiting their broader utilization. We have developed a simple but effective method based on Bernoulli's principle, the Coanda effect and MEMS processing to focus electrosprayed droplets and liberated gas-phase ions. We demonstrate a computer simulation and fabrication process for a micromachined air amplifier. The simulation results are used to optimize the geometry and to meet performance requirements. The optimized results then provide a design guideline for the device's fabrication. The air amplifier is formed from two bonded polydimethylsiloxane (PDMS) casts. Each PDMS cast is fabricated through a molding process using a micromachined two-layer SU-8 mold. Experimental results show a 30-fold improvement in the ES current for certain operation conditions while the air amplifier is incorporated in the nano-electrospray ionization (nano-ESI) process. Compared with traditional air amplifiers, the micro-electro-mechanical systems (MEMS) based air amplifier provides good performance while keeping the fabrication process simple and cost effective.

  11. A modified additivity rule for the calculation of electron impact ionization cross-section of molecules ABn

    NASA Astrophysics Data System (ADS)

    Deutsch, H.; Becker, K.; Mark, T. D.

    1997-11-01

    This paper describes a modified additivity rule for the calculation of electron impact ionization cross-sections of molecules and radicals of the form ABn(n = 1-6). This additivity rule incorporates weighting factors for the contributions to the molecular ionization cross-sections from the ionization cross-sections of the constituent atoms, which depend explicitly on the atomic radii and the effective number of atomic electrons. In a few special cases (hydrides where the other constituent atom has a radius smaller than the radius of the H atom and species where both constituent atoms have radii smaller than the radius of the H atom), the weighting factors can be simplified, so that they depend only on the atomic radii, i.e. on geometric effects. A comprehensive comparison of the predictions of this new modified additivity rule with available experimental data and with other theoretical predictions is presented.

  12. Molecular orientation effect on the differential cross sections for the electron-impact double ionization of oriented water molecules

    SciTech Connect

    Champion, C.; Dal Cappello, C.; Oubaziz, D.; Aouchiche, H.; Popov, Yu. V.

    2010-03-15

    Double ionization of isolated water molecules fixed in space is here investigated in a theoretical approach based on the first Born approximation. Secondary electron angular distributions are reported for particular (e,3e) kinematical conditions and compared in terms of shape and magnitude. Strong dependence of the fivefold differential cross sections on the molecular target orientation is clearly observed in (e,3-1e) as well as (e,3e) channels. Furthermore, for the major part of the kinematics considered, we identified the different mechanisms involved in the double ionization of water molecule, namely, the direct shake-off process as well as the two-step1 process. They are both discussed and analyzed with respect to the molecular target orientation.

  13. Predictable surface ablation of dielectrics with few-cycle laser pulse even beyond air ionization

    NASA Astrophysics Data System (ADS)

    Pasquier, C.; Sentis, M.; Utéza, O.; Sanner, N.

    2016-08-01

    We study surface ablation of dielectrics with single-shot few-cycle optical pulse (˜10 fs) in air, at intensities below and above the onset of air ionization. We perform 3D analysis and careful calibration of the fluence distribution at the laser focus, spanning from linear- to nonlinear- focusing regimes, enabling to thoroughly characterize the severe limitation of the fluence delivered onto the sample surface upon increase of incident pulse energy. Despite significant beam reshaping taking place at high fluence, we demonstrate that it is nevertheless possible to confidently predict the resulting crater profiles on fused silica surface, even in the regime of filamentation.

  14. Electrophysical and optophysical properties of air ionized by a short pulse of fast electrons

    NASA Astrophysics Data System (ADS)

    Vagin, Iu. P.; Stal', N. L.; Khokhlov, V. D.; Chernoiarskii, A. A.

    A method for solving the nonstationary kinetic equation of electron deceleration is developed which is based on the multigroup approximation. The electron distribution function in air ionized by nonstationary sources of primary electrons is determined, and the avalanche formation of secondary electrons is considered. Theoretical and experimental results are presented on the time dependence of the air luminescence intensity in two spectral intervals, one including the 391.4 nm N2(+) band and the other including the 337.1 nm N2 band, for different values of gas pressure under the effect of a short beam of electrons with energies of 100 keV.

  15. The influence of negative ionization of the air on motor activity in Syrian hamsters ( Masocricetus auratus Waterhouse) in light conditions

    NASA Astrophysics Data System (ADS)

    Lenkiewicz, Zofia; Dabrowska, Barbara; Schiffer, Zofia

    1989-12-01

    The motor activity of Syrian hamsters ( Mesocricetus auratus Waterhouse) under the influence of negative ionization of the atmosphere applied for 10, 20 or 30 min per day was investigated. An ionizer with output of 14000 light negative ions per 1 cm3 of air was used. Studies carried out in the light phase of a 12∶12 h light/dark regime revealed a relation between the reaction of the animal and the time of day at which ionization was applied. Ionization for 20 or 30 min in the light phase decreased motor activity, while 10 min of ionization increased it compared to control animals. Ionization in the dark phase gave a more distinct rise in activity than that applied in the light phase for all three durations of ionization.

  16. Ionization cross sections and rate coefficients for CFCl3 molecule by electron impact

    NASA Astrophysics Data System (ADS)

    Pal, Satyendra; Kumar, Neeraj

    2013-09-01

    Chlorofluorocarbons (CFCs) or freons are important industrial material with wide-ranging applications as refrigerant, aerosol propellant and semiconductor etchant, etc. The large-scale industrial consumption is of particular environmental concern because of its potential for ozone destruction in the stratosphere. The present work reports the calculations for differential cross sections as a function of secondary/ ejected electron energy and the scattering angle in the ionization of CFCl3 by electron collision leading to the production of various cations viz. CCl3+,CFCl2+,CCl2+,CFCl+, CCl+, Cl+, CF+, F+, and C+ through direct and dissociative ionization processes at a fixed incident electron energy of 200 eV. A modified Jain-Khare semi-empirical formalism based on oscillator strength has been employed. To the best of our knowledge, no experimental and/or theoretical data is available for comparison of the present results for differential cross sections. The corresponding derived integral cross sections in terms of the partial ionization cross sections corresponding to these cations, in the energy range varying from ionization threshold to 1000 eV, revealed a reasonably good agreement with the experimental and theoretical data, wherever available. In addition to the differential and integral ionization cross sections, we have also calculated the ionization rate coefficients using the evaluated partial ionization cross sections and the Maxwell-Boltzmann distribution as a function of electron energy.

  17. Laser desorption/ionization mass spectrometry for direct profiling and imaging of small molecules from raw biological materials

    SciTech Connect

    Cha, Sangwon

    2008-01-01

    Matrix-assisted laser desorption/ionization(MALDI) mass spectrometry(MS) has been widely used for analysis of biological molecules, especially macromolecules such as proteins. However, MALDI MS has a problem in small molecule (less than 1 kDa) analysis because of the signal saturation by organic matrixes in the low mass region. In imaging MS (IMS), inhomogeneous surface formation due to the co-crystallization process by organic MALDI matrixes limits the spatial resolution of the mass spectral image. Therefore, to make laser desorption/ionization (LDI) MS more suitable for mass spectral profiling and imaging of small molecules directly from raw biological tissues, LDI MS protocols with various alternative assisting materials were developed and applied to many biological systems of interest. Colloidal graphite was used as a matrix for IMS of small molecules for the first time and methodologies for analyses of small metabolites in rat brain tissues, fruits, and plant tissues were developed. With rat brain tissues, the signal enhancement for cerebroside species by colloidal graphite was observed and images of cerebrosides were successfully generated by IMS. In addition, separation of isobaric lipid ions was performed by imaging tandem MS. Directly from Arabidopsis flowers, flavonoids were successfully profiled and heterogeneous distribution of flavonoids in petals was observed for the first time by graphite-assisted LDI(GALDI) IMS.

  18. Probing photoelectron angular distributions in molecules with polarization-controlled two-color above-threshold ionization

    NASA Astrophysics Data System (ADS)

    Leitner, Torsten; Taïeb, Richard; Meyer, Michael; Wernet, Philippe

    2015-06-01

    We present polarization-controlled multiphoton two-color above-threshold ionization (TCATI) of molecules. The intensity modulations of valence photoelectron intensities of molecules arising from varying the relative orientation of the linear polarization vectors of femtosecond infrared (IR) and vacuum-ultraviolet (VUV) radiation in TCATI of the highest occupied molecular orbitals of H2O , O2, and N2 are reported. The results on the molecular systems are compared to the 3 p photoionization of atomic Ar, which serves as a reference system. Modeling the large differences of the modulation amplitudes within the soft-photon approximation enables us to extract the one-photon-ionization anisotropy parameter β2. Accounting only for the first sideband due to two-photon TCATI by one VUV and one IR photon we find satisfactory agreement between experiment and simulation for H2O and O2. However, the model fails for N2 and possible reasons are discussed. We discuss that the described approach may represent an alternative way of determining photoelectron angular distributions from valence shells of molecules and indicate future directions for modeling TCATI of molecules.

  19. Effects of autoionizing states on two-photon double ionization of the H2 molecule

    NASA Astrophysics Data System (ADS)

    Guan, Xiaoxu; Bartschat, Klaus; Koesterke, Lars; Schneider, Barry I.

    2014-04-01

    We report angle-resolved and angle-integrated cross sections for two-photon double-ionization of H by a strong laser pulse. The effect of doubly excited states on the predicted cross sections is addressed.

  20. Biomimetic air sampling for detection of low concentrations of molecules and bioagents : LDRD 52744 final report.

    SciTech Connect

    Hughes, Robert Clark

    2003-12-01

    Present methods of air sampling for low concentrations of chemicals like explosives and bioagents involve noisy and power hungry collectors with mechanical parts for moving large volumes of air. However there are biological systems that are capable of detecting very low concentrations of molecules with no mechanical moving parts. An example is the silkworm moth antenna which is a highly branched structure where each of 100 branches contains about 200 sensory 'hairs' which have dimensions of 2 microns wide by 100 microns long. The hairs contain about 3000 pores which is where the gas phase molecules enter the aqueous (lymph) phase for detection. Simulations of diffusion of molecules indicate that this 'forest' of hairs is 'designed' to maximize the extraction of the vapor phase molecules. Since typical molecules lose about 4 decades in diffusion constant upon entering the liquid phase, it is important to allow air diffusion to bring the molecule as close to the 'sensor' as possible. The moth acts on concentrations as low as 1000 molecules per cubic cm. (one part in 1e16). A 3-D collection system of these dimensions could be fabricated by micromachining techniques available at Sandia. This LDRD addresses the issues involved with extracting molecules from air onto micromachined structures and then delivering those molecules to microsensors for detection.

  1. Electrophysical and optophysical properties of air ionized by a short pulse of fast electrons

    SciTech Connect

    Vagin, Yu.P.; Stal', N.L.; Khokhlov, V.D.; Chernoyarskii, A.A.

    1987-12-01

    A method of solving the nonsteady kinetic equation of deceleration of electrons is developed in the basis of the application of the multigroup approximation. The electron distribution function in air ionized by nonsteady sources of primary electrons is determined, and the process of avalanche formation of secondary electrons in air is investigated. The time dependence of the emission intensity of air is determined, experimentally and by calculation, in two spectral intervals, one of which includes the lambda = 391.4 nm NS N/sub 2//sup +/ (O, O) band while the other includes the lambda = 337.1 nm 2 PS N/sub 2/ (O, O) band, under the action of a short electron beam with an energy E = 100 keV for different values of the gas pressure. The agreement between theoretical results and experimental data indicates the reliability of the method of solving the nonsteady kinetic equation of electron deceleration proposed in the paper.

  2. High-resolution ion pulse ionization chamber with air filling for the 222Rn decays detection

    NASA Astrophysics Data System (ADS)

    Gavrilyuk, Yu. M.; Gangapshev, A. M.; Gezhaev, A. M.; Etezov, R. A.; Kazalov, V. V.; Kuzminov, V. V.; Panasenko, S. I.; Ratkevich, S. S.; Tekueva, D. A.; Yakimenko, S. P.

    2015-11-01

    The construction and characteristics of the cylindrical ion pulse ionization chamber (CIPIC) with a working volume of 3.2 L are described. The chamber is intended to register α-particles from the 222Rn and its daughter's decays in the filled air sample. The detector is less sensitive to electromagnetic pick-ups and mechanical noises. The digital pulse processing method is proposed to improve the energy resolution of the ion pulse ionization chamber. An energy resolution of 1.6% has been achieved for the 5.49 MeV α-line. The dependence of the energy resolution on high voltage and working media pressure has been investigated and the results are presented.

  3. Impact of electron ionization on the generation of high-order harmonics from molecules

    SciTech Connect

    Brener, S.; Moiseyev, N.; Ivanov, M. V.

    2003-08-01

    When the laser frequency is tuned to be equal to the molecular electronic excitation, high-order harmonics are generated due to the electronic dipole transitions between the corresponding two potential-energy surfaces (PES). A natural, often taken, choice is the PES of the field-free molecular system. In this special choice the ionization phenomenon is not considered. Only the effect of the dissociation is considered. The method we developed enables one to remain within the framework of the 2-PES approximation and yet to include also the ionization effect in the calculations of molecular high-order harmonic generation spectra. In this approach the coupling between the electronic and nuclear motions is taken into consideration by using coupled complex adiabatic PES. As an illustrative numerical example, we calculated the high harmonic generation (HHG) spectra of H{sub 2}{sup +} in a 730-nm laser with the intensity of 8.77x10{sup 13} W/cm{sup 2}. The inclusion of the ionization in our approach not only enables the electrons to tunnel through the effective static potential barrier, but also apply an asymmetric force which accelerates the electron before ionization takes place. Therefore, indirectly the inclusion of the ionization by the laser field may lead eventually to an enhanced HHG spectra in comparison with the calculated one when the ''natural'' choice of the field-free 2PES is taken.

  4. The time-dependent generalized active space configuration interaction approach to correlated ionization dynamics of diatomic molecules

    NASA Astrophysics Data System (ADS)

    Bauch, S.; Larsson, H. R.; Hinz, C.; Bonitz, M.

    2016-03-01

    In this contribution, we review the time-dependent generalized-active-space configuration interaction (TD-GAS-CI) approach to the photoionization dynamics of atoms and molecules including electron correlation effects. It is based on the configuration interaction (CI) expansion of the many-body wave function and the restriction of the determinantal space to a reduced subspace. For its numerically efficient application to photoionization, a partially-rotated basis set is used which adopts features of a localized basis with a good reference description and a grid representation for escaping wave packets. After reviewing earlier applications of the theory, we address the strong-field ionization of a one-dimensional model of the four-electron LiH molecule using TD-GAS-CI and demonstrate the importance of electron-electron correlations in the ionization yield for different orientations of the molecule w.r.t the peak of the linearly polarized laser field. A pronounced orientation-dependent variation of the yield with the pulse duration and the level of considered electron-electron correlations is observed.

  5. Medium Vacuum Electron Emitter as Soft Atmospheric Pressure Chemical Ionization Source for Organic Molecules.

    PubMed

    Liedtke, Sascha; Ahlmann, Norman; Marggraf, Ulrich; Schütz, Alexander; Vautz, Wolfgang; Franzke, Joachim

    2016-05-01

    An electron emitter as a soft atmospheric pressure chemical ionization source is presented, which operates at inner pressures of the device in the medium vacuum range (>10(-3) hPa). Conventional nonradioactive electron emitters require high vacuum (<10(-6) hPa) to prevent electrical sparkovers. The emitter presented here contains structural modifications of an existing setup, which inhibits electrical breakdowns up to 10(-2) hPa at 8 kV acceleration voltage. The increased inner pressure reduces the ionization efficiency until 10(-3) hPa-achievable without a turbomolecular pump-by 2% compared to high-vacuum conditions. This can be compensated with an increase of the electron source output. The functionality of this ion source is demonstrated with mass spectrometric and ion mobility measurements of acetone, eucalyptol, and diisopropyl methanephosphonate. Additional mass spectrometric measurements of 20 different organic compounds demonstrate the soft characteristics of this ionization source. PMID:27046293

  6. Electron impact ionization in plasma technologies; studies on atomic boron and BN molecule

    NASA Astrophysics Data System (ADS)

    Joshi, Foram M.; Joshipura, K. N.; Chaudhari, Asha S.

    2016-05-01

    Electron impact ionization plays important role in plasma technologies. Relevant cross sections on atomic boron are required to understand the erosion processes in fusion experiments. Boronization of plasma exposed surfaces of tokomaks has proved to be an effective way to produce very pure fusion plasmas. This paper reports comprehensive theoretical investigations on electron scattering with atomic Boron and Boron Nitride in solid phases. Presently we determine total ionization cross-section Qion and the summed-electronic excitation cross section ΣQexc in a standard quantum mechanical formalism called SCOP and CSP-ic methods. Our calculated cross sections are examined as functions of incident electron energy along with available comparisons.

  7. Air Pollution, Obesity, Genes, and Cellular Adhesion Molecules

    PubMed Central

    Madrigano, Jaime; Baccarelli, Andrea; Wright, Robert O.; Suh, Helen; Sparrow, David; Vokonas, Pantel S.; Schwartz, Joel

    2011-01-01

    Objectives Particulate matter (PM) has been associated with acute cardiovascular outcomes, but our understanding of the mechanism is incomplete. We examined the association between PM and cell adhesion molecules. We also investigated the modifying effect of genotype and phenotype variation to gain insight into the relevant biological pathways for this association. Methods We used mixed regression models to examine the association of PM2.5 and black carbon (BC) with serum concentrations of soluble Intercellular Adhesion Molecule (sICAM-1) and soluble Vascular Cell Adhesion Molecule (sVCAM-1), markers of endothelial function and inflammation, in a longitudinal study of 809 participants in the Normative Aging Study (1819 total observations). We also examined whether this association was modified by genotype, obesity, or diabetes status. Genes selected for analyses were either related to oxidative stress, endothelial function, lipid metabolism or metal processing. Results BC during the 2 days prior to blood draw was significantly associated with increased sVCAM-1 (4.5% increase per 1μg/m3 95% CI 1.1, 8.0). Neither pollutant was associated with sICAM-1. Larger effects of BCon sVCAM were seen in subjects with obesity (p=0.007) and who were GSTM1 null (p=0.02). Conclusions BC is associated with markers of endothelial function and inflammation. Genes related to oxidative defense may modify this association. PMID:19884647

  8. Beam-loss monitoring system with free-air ionization chambers

    NASA Astrophysics Data System (ADS)

    Nakagawa, H.; Shibata, S.; Hiramatsu, S.; Uchino, K.; Takashima, T.

    1980-08-01

    A monitoring system for proton beam losses was installed in the proton synchrotron at the National Laboratory for High Energy Physics in Japan (KEK). The system consists of 56 air ionization chambers (AIC) for radiation detectors, 56 integrators, 56 variable gain amplifiers, two multiplexers, a computer interface circuit, a manual controller and a high tension power supply. The characteristics of the AIC, time resolution, radiation measurement upper limit saturation, kinetic energy dependence of the sensitivity, chamber activation effect, the beam loss detection system and the results of observations with the monitoring system are described.

  9. Experimental Determination of the Mass of Air Molecules from the Law of Atmospheres.

    ERIC Educational Resources Information Center

    Hayn, Carl H.; Galvin, Vincent, Jr.

    1979-01-01

    A gas pressure gauge has been constructed for use in a student experiment involving the law of atmospheres. From pressure data obtained at selected elevations the average mass of air molecules is determined and compared to that calculated from the molecular weights and percentages of constituents to the air. (Author/BB)

  10. A guideline for the identification of environmentally relevant, ionizable organic molecule species.

    PubMed

    Schaffer, Mario; Licha, Tobias

    2014-05-01

    An increasing number of organic compounds detected today in the aquatic environment are ionizable and, therefore, partially or permanently charged (ionic) under the pH conditions encountered in these systems. For evaluating their environmental behavior, which strongly depends on the charge state, the identification of functional groups together with their correct assignment of the respective acidic or basic dissociation constants (pKa) is essential. Despite the growing concern and increasing awareness for ionizable compounds, contradicting and/or confusing information regarding their acid/base properties can be regularly found in the literature, especially when complex structures are encountered. Therefore, we provide a simplified, general, and comprehensive guideline for the identification of ionizable functional groups in organic compounds combined with the correct assignment of their respective pKa values. Beside the explicit definition of basic terms, several tables with more than 30 of the most frequently encountered ionizable compound classes, including their typical pKa value ranges are the centerpiece of the proposed procedure. The straight forward application of the guideline is successfully shown for several environmentally relevant compounds as example. PMID:24412098

  11. A High-Pressure Hollow Cathode Ionization Source for In-Situ Detection of Organic Molecules

    NASA Technical Reports Server (NTRS)

    Beegle, L. W.; Kanik, I.

    2001-01-01

    We have designed, constructed and characterized a new high-pressure (1-5 Torr) hollow cathode discharge source (HCDS) that can be utilized as an ionizer in a wide variety of mass analyzers. Additional information is contained in the original extended abstract.

  12. Counting Molecules by Desorption Ionization and Mass Spectrometry/Mass Spectrometry.

    ERIC Educational Resources Information Center

    Cooks, R. G.; Busch, K. L.

    1982-01-01

    Discusses two newer methods in mass spectrometry and shows how they can increase signal and signal-to-noise ratios, respectively. The first method, desorption ionization (DI), increases sensitivity while the second method, mass spectrometry/mass spectrometry (MS/MS), increases specificity. Together, the two methods offer improved analytical…

  13. Multiphoton Ionization and Two-Photon Excitation of Aromatic Molecules in Liquids

    NASA Astrophysics Data System (ADS)

    Faidas, Homer

    1985-12-01

    The two-photon excitation of benzene and toluene in a number of different nonpolar liquids (n-pentane, tetramethylsilane, perfluoro-n-hexane, perfluoromethylcyclohexane, and perfluorodimethylcyclobutane) was studied over the 360-560 nm laser excitation wavelength range. The effect of the solvent on the upper excited states was investigated and a peak, observed in the two -photon excitation spectra of benzene, was assigned to the (3s)('1)E(,1g) Rydberg state based on the unusual solvent dependence of its relative intensity and spectral shift. Polarization studies and signal vs. laser intensity measurements were also carried out. Virbrational analyses of the entire range of the ('1)B(,2u) state of benzene and of the ('1)B(,2) state of toluene, including the hot bands, were performed based on the spectra measured in perfluoro-n-hexane. The O-O transitions of these states in perfluoro-n-hexane and n -pentane were observed at 38050 cm('-1) and 37853 cm('-1) for benzene and at 37411 cm('-1) and 37220 cm('-1) for toluene, respectively. The two-photon excitation spectrum of fluoranthene in a solution of n-pentane over the 420-860 nm laser excitation range was also measured. The O-O transition of the first singlet state was observed at 24800 cm('-1), resolving thus the ambiguity about the exact position of that state. The multiphoton ionization of benzene in dilute solutions of n-pentane and tetramethylsilane was also studied, over the 360-570 nm laser excitation range. Polarization studies and signal vs. laser intensity measurements were performed and the dependence of the spectral features and of the polarization ratio on the laser intensity was studied. The multiphoton ionization mechanism, the location of the ionization threshold of benzene in n-pentane and in tetramethylsilane and the effect of the medium on the ionization threshold are discussed. A particular ionization behavior was observed in a wavelength region corresponding to the channel 3 relaxation which

  14. Investigation of Ionization and Dissociation Processes Produced by Electron Impact on Molecules.

    NASA Astrophysics Data System (ADS)

    Ma, Ce.

    1990-01-01

    Absolute electron impact partial ionization cross sections for Ar and CF_4 were measured by use of a newly built pulsed electron beam time-of-flight apparatus for incident electron energies from thresholds to 500 eV. The apparatus employed consisted of a low energy electron gun, 40 mm diameter ion extraction gold screens, time-of-flight drift tubes, micro-channel plate detectors and fast time to digital electronics. A pulsed electron beam was obtained by pulsing the control grid of the electron gun. Both beam - beam experiments and beam - constant gas target pressure experiments were carried out to determine the absolute partial ionization cross sections for Ar ^{+}, Ar^{2+ }, Ar^{3+} from an argon gas target, and for CF_sp {3}{+}, CF_sp {2}{+}, CF_sp {3}{2+}, CF^ {+}, CF_sp{2} {2+}, F^{+}, C^{+} from a CF _4 gas target. By charge weighted summing of the partial ionization cross sections, the total ionization cross sections of Ar and CF_4 were obtained. The total neutral dissociation cross section for CF_4 was inferred from the total ionization cross section and the total dissociation cross section. Also, a new method for determining absolute total electron scattering cross sections with corrections for forward scattering was developed. The electron beam current was measured as function of gas target pressure and the scattering path length. The total electron scattering cross section obtained from the new model is as much as 6% larger than the cross section derived from the traditional Beer's law for Ar at an incident electron energy of 300 eV. This method is capable of yielding reliable total cross section up to 10 keV. Finally, a study of the secondary electron emission as a function of ejection angle and ejection energy for CO, the doubly differential cross section (DDCS), is presented.

  15. Electron-correlation effects in enhanced ionization of molecules: A time-dependent generalized-active-space configuration-interaction study

    NASA Astrophysics Data System (ADS)

    Chattopadhyay, S.; Bauch, S.; Madsen, L. B.

    2015-12-01

    We numerically study models of H2 and LiH molecules, aligned collinearly with the linear polarization of the external field, to elucidate the possible role of correlation in the enhanced-ionization (EI) phenomena. Correlation is considered at different levels of approximation with the time-dependent generalized-active-space configuration-interaction method. The results of our studies show that enhanced ionization occurs in multielectron molecules and that correlation is important, and they also demonstrate significant deviations between the results of the single-active-electron approximation and more accurate configuration-interaction methods. We further investigate the role of low-lying excited states in the EI phenomena. With the inclusion of correlation we show strong carrier-envelope-phase effects in the enhanced ionization of the asymmetric heteronuclear LiH -like molecule. The correlated calculation shows an intriguing feature of crossover in enhanced ionization with two carrier-envelope phases at critical internuclear separation.

  16. Application of the modified additivity rule to the calculation of electron-impact ionization cross sections of complex molecules

    SciTech Connect

    Deutsch, H.; Becker, K.; Basner, R.; Schmidt, M.; Maerk, T.D.

    1998-11-05

    This paper describes the application of the modified additivity rule (MAR) to the calculation of total (counting) electron-impact ionization cross sections of complex molecules with sum formulas of the form A{sub x},B{sub y}, A{sub x},B{sub y},C{sub z}, and A{sub p},B{sub s}C{sub t}D{sub u}. The MAR incorporates weighting factors for the contributions to the molecular ionization cross section from the ionization cross sections of the constituent atoms, which depend explicitly on the atomic radii and the effective number of atomic electrons except for a few special cases (hydrides where the other constituent atom has a radius smaller than the radius of the H atom and species where both constituent atoms have radii smaller than the radius of the H atom), where the weighting factors depend only on the atomic radii, i.e., on geometric effects. A comprehensive comparison of the predictions of the modified additivity rule with available experimental data and with other theoretical predictions is presented.

  17. Field ionization of high-Rydberg fragments produced after inner-shell photoexcitation and photoionization of the methane molecule

    NASA Astrophysics Data System (ADS)

    Kivimäki, A.; Sankari, A.; Kettunen, J. A.; Strâhlman, C.; Álvarez Ruiz, J.; Richter, R.

    2015-09-01

    We have studied the production of neutral high-Rydberg (HR) fragments from the CH4 molecule at the C 1s → 3p excitation and at the C 1s ionization threshold. Neutral fragments in HR states were ionized using a pulsed electric field and the resulting ions were mass-analyzed using an ion time-of-flight spectrometer. The atomic fragments C(HR) and H(HR) dominated the spectra, but molecular fragments CHx(HR), x = 1-3, and H2(HR) were also observed. The production of HR fragments is attributed to dissociation of CH4+ and CH42+ ions in HR states. Just above the C 1s ionization threshold, such molecular ionic states are created when the C 1s photoelectron is recaptured after single or double Auger decay. Similar HR states may be reached directly following resonant Auger decay at the C 1s → 3p resonance. The energies and geometries of the parent and fragment ions have been calculated in order to gain insight into relevant dissociation pathways.

  18. K-shell and total ionization cross sections following electron-molecule collisions: An empirical scaling law

    SciTech Connect

    Fremont, F.; Hajaji, A.; Chesnel, J.-Y.

    2006-11-15

    Collisions between electrons and various molecular targets (H{sub 2}O, CH{sub 4}, C{sub 3}H{sub 4}, N{sub 2}) at projectile energies above the K-shell ionization threshold of the molecule have been investigated experimentally. From electron emission spectra, relative total ionization cross section {sigma}{sub t} and K-shell ionization cross section {sigma}{sub K} are determined. The ratio {sigma}{sub K}/{sigma}{sub t} is then deduced for each target as a function of the projectile energy and compared with those evaluated in the case of atomic targets. Strong differences between atomic and molecular targets are observed in the slope of the ratio at the highest projectile energies. These differences are explained using the well-known Kim-Rudd formula developed for atomic targets. In the projectile energy range we explored, we develop a simple empirical scaling law for the ratio {sigma}{sub K}/{sigma}{sub t} as a function of the projectile energy.

  19. Field ionization of high-Rydberg fragments produced after inner-shell photoexcitation and photoionization of the methane molecule

    SciTech Connect

    Kivimäki, A.; Sankari, A.; Kettunen, J. A.; Stråhlman, C.; Álvarez Ruiz, J.; Richter, R.

    2015-09-21

    We have studied the production of neutral high-Rydberg (HR) fragments from the CH{sub 4} molecule at the C 1s → 3p excitation and at the C 1s ionization threshold. Neutral fragments in HR states were ionized using a pulsed electric field and the resulting ions were mass-analyzed using an ion time-of-flight spectrometer. The atomic fragments C(HR) and H(HR) dominated the spectra, but molecular fragments CH{sub x}(HR), x = 1-3, and H{sub 2}(HR) were also observed. The production of HR fragments is attributed to dissociation of CH{sub 4}{sup +} and CH{sub 4}{sup 2+} ions in HR states. Just above the C 1s ionization threshold, such molecular ionic states are created when the C 1s photoelectron is recaptured after single or double Auger decay. Similar HR states may be reached directly following resonant Auger decay at the C 1s → 3p resonance. The energies and geometries of the parent and fragment ions have been calculated in order to gain insight into relevant dissociation pathways.

  20. Ion/molecule reactions of arsenic and phosphorus cluster ions: Ionization potentials and novel reaction pathways

    SciTech Connect

    Zimmerman, J.A.; Bach, S.B.H.; Watson, C.H.; Eyler, J.R. )

    1991-01-10

    Ionization potentials (IP's) for arsenic and phosphorus clusters (As{sub n}, n = 1-5; P{sub n}, n = 1-4) have been determined by gas-phase charge-transfer reactions. Arsenic and phosphorus cluster ions were generated by pulsed CO{sub 2} laser desorption from GaAs and InP substrates, mass-selected, thermalized, and allowed to react with compounds of known ionization potential in a Fourier transform ion cyclotron resonance mass spectrometer. The IP's for As{sub 3} and As{sub 5} previously unreported, as well as more accurate IP values for several of the other clusters, have been determined. Products and rate coefficients of some interesting reactions of the cluster ions with the charge-transfer agents are also reported.

  1. Auger ionization beats photo-oxidation of semiconductor quantum dots: extended stability of single-molecule photoluminescence.

    PubMed

    Yamashita, Shin-Ichi; Hamada, Morihiko; Nakanishi, Shunsuke; Saito, Hironobu; Nosaka, Yoshio; Wakida, Shin-Ichi; Biju, Vasudevanpillai

    2015-03-23

    Despite the bright and tuneable photoluminescence (PL) of semiconductor quantum dots (QDs), the PL instability induced by Auger recombination and oxidation poses a major challenge in single-molecule applications of QDs. The incomplete information about Auger recombination and oxidation is an obstacle in the resolution of this challenge. Here, we report for the first time that Auger-ionized QDs beat self-sensitized oxidation and the non-digitized PL intensity loss. Although high-intensity photoactivation insistently induces PL blinking, the transient escape of QDs into the ultrafast Auger recombination cycle prevents generation of singlet oxygen ((1) O2 ) and preserves the PL intensity. By the detection of the NIR phosphorescence of (1) O2 and evaluation of the photostability of single QDs in aerobic, anaerobic, and (1) O2 scavenger-enriched environments, we disclose relations of Auger ionization and (1) O2 -mediated oxidation to the PL stability of single QDs, which will be useful during the formulation of QD-based single-molecule imaging tools and single-photon devices.

  2. Anion Effects on Sodium Ion and Acid Molecule Adduction to Protein Ions in Electrospray Ionization Mass Spectrometry

    PubMed Central

    Flick, Tawnya G.; Merenbloom, Samuel I.; Williams, Evan R.

    2012-01-01

    Gaseous protein–metal ion and protein–molecule complexes can be readily formed by electrospray ionization (ESI) from aqueous solutions containing proteins and millimolar concentrations of sodium salts of various anions. The extent of sodium and acid molecule adduction to multiply charged protein ions is inversely related and depends strongly on the proton affinity (PA) of the anion, with extensive sodium adduction occurring for anions with PA values greater than ~300 kcal·mol−1 and extensive acid molecule adduction occurring for anions with PA values less than 315 kcal·mol−1. The role of the anion on the extent of sodium and acid molecule adduction does not directly follow the Hofmeister series, suggesting that direct protein–ion interactions may not play a significant role in the observed effect of anions on protein structure in solution. These results indicate that salts with anions that have low PA values may be useful solution-phase additives to minimize nonspecific metal ion adduction in ESI experiments designed to identify specific protein-metal ion interactions. PMID:21952761

  3. Classical trajectory Monte Carlo model calculations for ionization of the uracil molecule by impact of heavy ions

    NASA Astrophysics Data System (ADS)

    Sarkadi, L.

    2016-09-01

    The ionization of the uracil molecule induced by heavy-ion impact has been investigated using the classical trajectory Monte Carlo (CTMC) method. Assuming the validity of the independent-particle model approximation, the collision problem is solved by considering the three-body dynamics of the projectile, an active electron and the molecule core. The interaction of the molecule core with the other two particles is described by a multi-center potential built from screened atomic potentials. The cross section differential with respect to the energy and angle of the electrons ejected in the ionization process has been calculated for an impact of 3.5 MeV u-1 {{{C}}}6+ ions. Total electron emission cross sections (TCS) are presented for {{{C}}}q+ (q=0-6) and {{{O}}}6+ projectiles as a function of the impact energy in the range from 10 keV u-1 to 10 MeV u-1. The dependence of the TCS on the charge state of the projectile has been investigated for 2.5 MeV u-1 {{{O}}}q+ (q=4-8) and {{{F}}}q+ (q=5-9) ions. The results of the calculations are compared with available experimental data and the predictions of other theoretical models: the first Born approximation with correct boundary conditions (CB1), the continuum-distorted-wave-eikonal-initial-state approach (CDW-EIS), and the combined classical-trajectory Monte Carlo-classical over-the-barrier model (CTMC-COB).

  4. Classical trajectory Monte Carlo model calculations for ionization of the uracil molecule by impact of heavy ions

    NASA Astrophysics Data System (ADS)

    Sarkadi, L.

    2016-09-01

    The ionization of the uracil molecule induced by heavy-ion impact has been investigated using the classical trajectory Monte Carlo (CTMC) method. Assuming the validity of the independent-particle model approximation, the collision problem is solved by considering the three-body dynamics of the projectile, an active electron and the molecule core. The interaction of the molecule core with the other two particles is described by a multi-center potential built from screened atomic potentials. The cross section differential with respect to the energy and angle of the electrons ejected in the ionization process has been calculated for an impact of 3.5 MeV u‑1 {{{C}}}6+ ions. Total electron emission cross sections (TCS) are presented for {{{C}}}q+ (q=0-6) and {{{O}}}6+ projectiles as a function of the impact energy in the range from 10 keV u‑1 to 10 MeV u‑1. The dependence of the TCS on the charge state of the projectile has been investigated for 2.5 MeV u‑1 {{{O}}}q+ (q=4-8) and {{{F}}}q+ (q=5-9) ions. The results of the calculations are compared with available experimental data and the predictions of other theoretical models: the first Born approximation with correct boundary conditions (CB1), the continuum-distorted-wave–eikonal-initial-state approach (CDW-EIS), and the combined classical-trajectory Monte Carlo–classical over-the-barrier model (CTMC-COB).

  5. Attosecond control of dissociative ionization of O{sub 2} molecules

    SciTech Connect

    Siu, W.; Kelkensberg, F.; Gademann, G.; Rouzee, A.; Vrakking, M. J. J.; Johnsson, P.; Dowek, D.; Lucchini, M.; Calegari, F.; De Giovannini, U.; Rubio, A.; Lucchese, R. R.; Kono, H.; Lepine, F.

    2011-12-15

    We demonstrate that dissociative ionization of O{sub 2} can be controlled by the relative delay between an attosecond pulse train (APT) and a copropagating infrared (IR) field. Our experiments reveal a dependence of both the branching ratios between a range of electronic states and the fragment angular distributions on the extreme ultraviolet (XUV) to IR time delay. The observations go beyond adiabatic propagation of dissociative wave packets on IR-induced quasistatic potential energy curves and are understood in terms of an IR-induced coupling between electronic states in the molecular ion.

  6. Photoionization Dynamics and Ion State Distributions in Single-Photon and Resonance-Enhanced Multiphoton Ionization of Molecules.

    NASA Astrophysics Data System (ADS)

    Braunstein, Matthew

    This thesis presents results of theoretical studies of single-photon ionization and resonance enhanced multiphoton ionization (REMPI) of several small molecules. The first part of the thesis examines shape resonances in the photoionization of O_2. Studies reported here include investigations of branching ratios of electronic multiplet states in the 3sigma _{g} and 1pi_ {u} photoionization of O_2 and a comparison of photoionization of the singlet states, a ^1Delta_{g} and d ^1prod_{g } (3ssigma_{g} 1pi_{g}), with that of the ground state of O_2. These studies show that the electronic exchange interaction between the ion core and the photoelectron in shape resonant energy regions profoundly affects the electronic state distributions of the molecular ion. We also report vibrational branching ratios in the single-photon ionization of O_2 , and in REMPI of O_2 via the G^3prod_{g} Rydberg state. In these studies, we find that a shape resonance causes a dependence of the electronic transition moment on the molecular geometry leading to non-Franck -Condon ion vibrational distributions and a dependence of the rotational branch intensity on the ion vibrational state. The second part of this thesis examines shape resonances in other molecules, focusing on the more general aspects of the photoionization dynamics. Here we present studies of the vibrational state distributions in the 7 sigma photoionization of the polyatomic N_2O, where a shape resonance causes non-Franck-Condon vibrational state distributions, the degree of which depends on the nuclear displacements involved and whether the shape resonance is localized on a particular bond. We also study the photoionization dynamics of the valence shell of Cl_2, where a shape resonance is also seen. Finally, we present studies of the K-shell ionization of CO. Studies in this energy region have assumed a new importance with the development of tunable X-ray synchrotron sources. Here, electronic relaxation in the production of a K

  7. Formation and Fragmentation of Protonated Molecules after Ionization of Amino Acid and Lactic Acid Clusters by Collision with Ions in the Gas Phase.

    PubMed

    Poully, Jean-Christophe; Vizcaino, Violaine; Schwob, Lucas; Delaunay, Rudy; Kocisek, Jaroslav; Eden, Samuel; Chesnel, Jean-Yves; Méry, Alain; Rangama, Jimmy; Adoui, Lamri; Huber, Bernd

    2015-08-01

    Collisions between O(3+) ions and neutral clusters of amino acids (alanine, valine and glycine) as well as lactic acid are performed in the gas phase, in order to investigate the effect of ionizing radiation on these biologically relevant molecular systems. All monomers and dimers are found to be predominantly protonated, and ab initio quantum-chemical calculations on model systems indicate that for amino acids, this is due to proton transfer within the clusters after ionization. For lactic acid, which has a lower proton affinity than amino acids, a significant non-negligible amount of the radical cation monomer is observed. New fragment-ion channels observed from clusters, as opposed to isolated molecules, are assigned to the statistical dissociation of protonated molecules formed upon ionization of the clusters. These new dissociation channels exhibit strong delayed fragmentation on the microsecond time scale, especially after multiple ionization.

  8. Influence of ionizing irradiation in air and nitrogen for sterilization of surgical grade polyethylene for implants

    NASA Astrophysics Data System (ADS)

    Streicher, R. M.

    The influence of the atmosphere and the applied dose during ionizing radiation treatment on selected properties of ultra high molecular weight polyethylene (UHMWPE) have been investigated. A linear correlation between extinction coefficient and applied dosis in air from 6 to 125 kGy was found, while oxidation was not linear with irradiation in nitrogen. Bacteria survival rate shows a necessary minimum dose of 15 kGy for assured sterility of the product. Post reaction of latent free radicals in UHMWPE created during irradiation, which react or recombine time- and environment dependent, has also been investigated after storage of UHMWPE-films in air and nitrogen at 21°C and in water at body temperature 37°C for up to nine months. Results show that the properties of UHMWPE after radiation-sterilization change depending on time, the absorbed dose, the atmosphere where irradiation took place and the environment of storage. UHMWPE, which mainly crosslinks during irradiation degrades by an oxidation process after sterilizing when stored in air and even more in water at body temperature. So irradiation and storage in nitrogen before implantation in the human body is beneficial.

  9. Quantitative mass spectrometry imaging of small-molecule neurotransmitters in rat brain tissue sections using nanospray desorption electrospray ionization.

    PubMed

    Bergman, Hilde-Marléne; Lundin, Erik; Andersson, Malin; Lanekoff, Ingela

    2016-06-01

    Small molecule neurotransmitters are essential for the function of the nervous system, and neurotransmitter imbalances are often connected to neurological disorders. The ability to quantify such imbalances is important to provide insights into the biochemical mechanisms underlying the disorder. This proof-of-principle study presents online quantification of small molecule neurotransmitters, specifically acetylcholine, γ-aminobutyric acid (GABA) and glutamate, in rat brain tissue sections using nanospray desorption electrospray ionization (nano-DESI) mass spectrometry imaging. By incorporating deuterated internal standards in the nano-DESI solvent we show identification, accurate mapping, and quantification of these small neurotransmitters in rat brain tissue without introducing any additional sample preparation steps. We find that GABA is about twice as abundant in the medial septum-diagonal band complex (MSDB) as in the cortex, while glutamate is about twice as abundant in the cortex as compared to the MSDB. The study shows that nano-DESI is well suited for imaging of small molecule neurotransmitters in health and disease. PMID:26859000

  10. Recommended direct simulation Monte Carlo collision model parameters for modeling ionized air transport processes

    NASA Astrophysics Data System (ADS)

    Swaminathan-Gopalan, Krishnan; Stephani, Kelly A.

    2016-02-01

    A systematic approach for calibrating the direct simulation Monte Carlo (DSMC) collision model parameters to achieve consistency in the transport processes is presented. The DSMC collision cross section model parameters are calibrated for high temperature atmospheric conditions by matching the collision integrals from DSMC against ab initio based collision integrals that are currently employed in the Langley Aerothermodynamic Upwind Relaxation Algorithm (LAURA) and Data Parallel Line Relaxation (DPLR) high temperature computational fluid dynamics solvers. The DSMC parameter values are computed for the widely used Variable Hard Sphere (VHS) and the Variable Soft Sphere (VSS) models using the collision-specific pairing approach. The recommended best-fit VHS/VSS parameter values are provided over a temperature range of 1000-20 000 K for a thirteen-species ionized air mixture. Use of the VSS model is necessary to achieve consistency in transport processes of ionized gases. The agreement of the VSS model transport properties with the transport properties as determined by the ab initio collision integral fits was found to be within 6% in the entire temperature range, regardless of the composition of the mixture. The recommended model parameter values can be readily applied to any gas mixture involving binary collisional interactions between the chemical species presented for the specified temperature range.

  11. A Device for Precision Neutralization of Electric Charge of Small Drops Using Ionized Air

    SciTech Connect

    Fan, Sewan

    2003-03-17

    For use in our Millikan type liquid drop searches for fractional charge elementary particles we have developed a simple ionized air device for neutralizing a narrow stream of small drops. The neutralizer has been used for drops ranging in diameter from 10 to 25 {micro}m. The width of the produced charge distribution is given by the Boltzmann equilibrium charge distribution and the mean of the distribution is set by a bias voltage. Using the bias voltage, the mean can be set with a precision of better than e, the electron charge. The use of the neutralizer is illustrated in an application to mineral oil drops produced with charges of the order of 1000e. We also show the interesting case of silicone oil drops that are produced in our drop generator with a charge distribution narrower than the Boltzmann equilibrium charge distribution, the charge distribution being broadened by the neutralizer.

  12. Developing repeatable measurements for reliable analysis of molecules at surfaces using desorption electrospray ionization.

    PubMed

    Green, F M; Stokes, P; Hopley, C; Seah, M P; Gilmore, I S; O'Connor, G

    2009-03-15

    Desorption electrospray ionization (DESI) is a powerful ambient ionization technique that can provide high-sensitivity mass spectrometry information directly from surfaces at ambient pressure. Although a growing amount of research has been devoted to exploring different applications, there are few studies investigating the basic parameters and underpinning metrology. An understanding of these is crucial to develop DESI as the robust and reliable technique required for significant uptake by industry. In this work, we begin with a systematic study of the parameters affecting the repeatability, sensitivity, and rate of consumption of material with DESI. To do this we have developed a model sample consisting of a thin uniform film of controlled thickness of Rhodamine B on glass. This model sample allowed assessment of optimal sensitivity and spot shape under different conditions. In addition, it allowed us to study the surface in more detail to understand why and how each parameter affects these. Using the model sample to optimize the instrument parameters for DESI led to an absolute intensity repeatability of better than 15%, achieved over a period of 1 day. This model sample provides valuable insight into the electrospray-sample interaction and the desorption mechanism. Confocal microscopy of areas analyzed by DESI allow droplet distribution, material utilization, and spot size to be determined. Studying surface erosion also gives the erosion rate of material, analogous to the sputtering yield in secondary ion mass spectrometry. The results of the study provide a clear description that explains the differences observed with changing electrospray parameters allowing optimization of the technique, for both spatial resolution and sensitivity. PMID:19281262

  13. Multiphoton ionization and fragmentation of iodine-containing molecules by femtosecond ultraintense hard X-rays

    NASA Astrophysics Data System (ADS)

    Robatjazi, S. J.; Li, X.; Rolles, D.; Rudenko, A.; Erk, B.; Boll, R.; Bomme, C.; Savelyev, E.; Rudek, B.; Foucar, L.; Bostedt, Ch.; Southworth, S.; Lehmann, C. S.; Kraessig, B.; Young, L.; Marchenko, T.; Simon, M.; Ueda, K.; Ferguson, K. R.; Bucher, M.; Gorkhover, T.; Carron, S.; Alonso-Mori, R.; Williams, G.; Boutet, S.

    2016-05-01

    We present ion charge state distributions and kinetic energy spectra resulting from the breakup of CH3 I and C6 H5 I molecules induced by femtosecond X-ray pulses from the Linac Coherent Light Source (LCLS) at 8.3 keV photon energy. Using a few-hundred nm focus of the LCLS CXI beamline, we reach peak intensities of up to 1020 W/ cm2, resulting in stripping of more than 50 electrons per molecule within few tens of fs. We find that in this regime the interplay between multiphoton absorption and subsequent charge rearrangement considerably differs from earlier observations for soft X-rays or for weaker hard X-rays. We discuss the pulse duration dependence of the data, and compare the results for seeded and unseeded LCLS pulses. Supported by the Chemical Sciences, Geosciences, and Biosciences Division, Office of Basic Energy Sciences, Office of Science, U. S. DOE.

  14. Charge transfer in dissociating iodomethane and fluoromethane molecules ionized by intense femtosecond X-ray pulses

    PubMed Central

    Boll, Rebecca; Erk, Benjamin; Coffee, Ryan; Trippel, Sebastian; Kierspel, Thomas; Bomme, Cédric; Bozek, John D.; Burkett, Mitchell; Carron, Sebastian; Ferguson, Ken R.; Foucar, Lutz; Küpper, Jochen; Marchenko, Tatiana; Miron, Catalin; Patanen, Minna; Osipov, Timur; Schorb, Sebastian; Simon, Marc; Swiggers, Michelle; Techert, Simone; Ueda, Kiyoshi; Bostedt, Christoph; Rolles, Daniel; Rudenko, Artem

    2016-01-01

    Ultrafast electron transfer in dissociating iodomethane and fluoromethane molecules was studied at the Linac Coherent Light Source free-electron laser using an ultraviolet-pump, X-ray-probe scheme. The results for both molecules are discussed with respect to the nature of their UV excitation and different chemical properties. Signatures of long-distance intramolecular charge transfer are observed for both species, and a quantitative analysis of its distance dependence in iodomethane is carried out for charge states up to I21+. The reconstructed critical distances for electron transfer are in good agreement with a classical over-the-barrier model and with an earlier experiment employing a near-infrared pump pulse. PMID:27051675

  15. Charge transfer in dissociating iodomethane and fluoromethane molecules ionized by intense femtosecond X-ray pulses.

    PubMed

    Boll, Rebecca; Erk, Benjamin; Coffee, Ryan; Trippel, Sebastian; Kierspel, Thomas; Bomme, Cédric; Bozek, John D; Burkett, Mitchell; Carron, Sebastian; Ferguson, Ken R; Foucar, Lutz; Küpper, Jochen; Marchenko, Tatiana; Miron, Catalin; Patanen, Minna; Osipov, Timur; Schorb, Sebastian; Simon, Marc; Swiggers, Michelle; Techert, Simone; Ueda, Kiyoshi; Bostedt, Christoph; Rolles, Daniel; Rudenko, Artem

    2016-07-01

    Ultrafast electron transfer in dissociating iodomethane and fluoromethane molecules was studied at the Linac Coherent Light Source free-electron laser using an ultraviolet-pump, X-ray-probe scheme. The results for both molecules are discussed with respect to the nature of their UV excitation and different chemical properties. Signatures of long-distance intramolecular charge transfer are observed for both species, and a quantitative analysis of its distance dependence in iodomethane is carried out for charge states up to I(21+). The reconstructed critical distances for electron transfer are in good agreement with a classical over-the-barrier model and with an earlier experiment employing a near-infrared pump pulse. PMID:27051675

  16. Screening of the Binding of Small Molecules to Proteins by Desorption Electrospray Ionization Mass Spectrometry Combined with Protein Microarray

    NASA Astrophysics Data System (ADS)

    Yao, Chenxi; Wang, Tao; Zhang, Buqing; He, Dacheng; Na, Na; Ouyang, Jin

    2015-11-01

    The interaction between bioactive small molecule ligands and proteins is one of the important research areas in proteomics. Herein, a simple and rapid method is established to screen small ligands that bind to proteins. We designed an agarose slide to immobilize different proteins. The protein microarrays were allowed to interact with different small ligands, and after washing, the microarrays were screened by desorption electrospray ionization mass spectrometry (DESI MS). This method can be applied to screen specific protein binding ligands and was shown for seven proteins and 34 known ligands for these proteins. In addition, a high-throughput screening was achieved, with the analysis requiring approximately 4 s for one sample spot. We then applied this method to determine the binding between the important protein matrix metalloproteinase-9 (MMP-9) and 88 small compounds. The molecular docking results confirmed the MS results, demonstrating that this method is suitable for the rapid and accurate screening of ligands binding to proteins.

  17. Double differential distribution of electron emission in the ionization of water molecules by fast bare oxygen ions

    NASA Astrophysics Data System (ADS)

    Bhattacharjee, Shamik; Biswas, Shubhadeep; Bagdia, Chandan; Roychowdhury, Madhusree; Nandi, Saikat; Misra, Deepankar; Monti, J. M.; Tachino, C. A.; Rivarola, R. D.; Champion, C.; Tribedi, Lokesh C.

    2016-03-01

    The doubly differential distributions of low-energy electron emission in the ionization of water molecules under the impact of fast bare oxygen ions with energy of 48 MeV are measured. The measured data are compared with two quantum-mechanical models, i.e. the post and prior versions of the continuum distorted wave-eikonal initial state (CDW-EIS) approximation, and the first-order Born approximation with initial and final wavefunctions verifying correct boundary conditions (CB1). An overall excellent qualitative agreement is found between the data and the CDW-EIS models whereas the CB1 model showed substantial deviation. However, the detailed angular distributions display some discrepancies with both CDW-EIS models. The single differential and total cross-sections exhibit good agreement with the CDW-EIS models. The present detailed data set could also be used as an input for modeling highly charged ion induced radiation damage in living tissues, whose most abundant component is water. Similar measurements are also carried out for a projectile energy of 60 MeV. However, since the double differential cross-section data show similar results the details are not provided here, except for the total ionization cross-sections results.

  18. Sensitive monitoring of volatile chemical warfare agents in air by atmospheric pressure chemical ionization mass spectrometry with counter-flow introduction.

    PubMed

    Seto, Yasuo; Kanamori-Kataoka, Mieko; Tsuge, Koichiro; Ohsawa, Isaac; Iura, Kazumitsu; Itoi, Teruo; Sekiguchi, Hiroyuki; Matsushita, Koji; Yamashiro, Shigeharu; Sano, Yasuhiro; Sekiguchi, Hiroshi; Maruko, Hisashi; Takayama, Yasuo; Sekioka, Ryoji; Okumura, Akihiko; Takada, Yasuaki; Nagano, Hisashi; Waki, Izumi; Ezawa, Naoya; Tanimoto, Hiroyuki; Honjo, Shigeru; Fukano, Masumi; Okada, Hidehiro

    2013-03-01

    A new method for sensitively and selectively detecting chemical warfare agents (CWAs) in air was developed using counter-flow introduction atmospheric pressure chemical ionization mass spectrometry (MS). Four volatile and highly toxic CWAs were examined, including the nerve gases sarin and tabun, and the blister agents mustard gas (HD) and Lewisite 1 (L1). Soft ionization was performed using corona discharge to form reactant ions, and the ions were sent in the direction opposite to the airflow by an electric field to eliminate the interfering neutral molecules such as ozone and nitrogen oxide. This resulted in efficient ionization of the target CWAs, especially in the negative ionization mode. Quadrupole MS (QMS) and ion trap tandem MS (ITMS) instruments were developed and investigated, which were movable on the building floor. For sarin, tabun, and HD, the protonated molecular ions and their fragment ions were observed in the positive ion mode. For L1, the chloride adduct ions of L1 hydrolysis products were observed in negative ion mode. The limit of detection (LOD) values in real-time or for a 1 s measurement monitoring the characteristic ions were between 1 and 8 μg/m(3) in QMS instrument. Collision-induced fragmentation patterns for the CWAs were observed in an ITMS instrument, and optimized combinations of the parent and daughter ion pairs were selected to achieve real-time detection with LOD values of around 1 μg/m(3). This is a first demonstration of sensitive and specific real-time detection of both positively and negatively ionizable CWAs by MS instruments used for field monitoring. PMID:23339735

  19. Comparison of Air Fluorescence and Ionization Measurements of E.M. Shower Depth Profiles: Test of a UHECR Detector Technique

    SciTech Connect

    Belz, J.; Cao, Z.; Huentemeyer, P.; Jui, C.C.H.; Martens, K.; Matthews, J.; Maestas, M.; Smith, J.; Sokolsky, P.; Springer, R.W.; Thomas, J.; Thomas, S.; Chen, P.; Field, Clive; Hast, C.; Iverson, R.; Ng, J.S.T.; Odian, A.; Reil, K.; Vincke, H.; Walz, D.; /SLAC /Montana U. /Rutgers U., Piscataway /Taiwan, Natl. Taiwan U.

    2005-10-07

    Measurements are reported on the fluorescence of air as a function of depth in electromagnetic showers initiated by bunches of 28.5 GeV electrons. The light yield is compared with the expected and observed depth profiles of ionization in the showers. It validates the use of atmospheric fluorescence profiles in measuring ultra high energy cosmic rays.

  20. Developments and Applications of Electrophoresis and Small Molecule Laser Desorption Ionization Mass Spectrometry

    SciTech Connect

    Zhang, Hui

    2007-01-01

    Ultra-sensitive native fluorescence detection of proteins with miniaturized one- and two-dimensional polyacrylamide gel electrophoresis was achieved with laser side-entry excitation, which provides both high excitation power and low background level. The detection limit for R-phycoerythrin protein spots in 1-D SDS-PAGE was as low as 15 fg, which corresponds to 40 thousand molecules only. The average detection limit of six standard native proteins was 5 pg per band and the dynamic range spanned more than 3 orders of magnitude. Approximately 150 protein spots from 30 ng of total Escherichia coli extraction were detected on a 0.8 cm x 1 cm gel in two-dimensional separation. Estrogen-DNA adducts as 4-OHE1(E2)-1-N3Ade and 4-OHEI(E2)-2-NacCys were hypothesized as early risk assessment of prostate and breast cancers. Capillary electrophoresis, luminescence/absorption spectroscopy and LC-MS were used to characterize and detect these adducts. Monoclonal antibodies against each individual adduct were developed and used to enrich such compounds from urine samples of prostate and breast cancer patients as well as healthy people. Adduct 4-OHE1-1-N3Ade was detected at much higher level in urine from subjects with prostate cancer patients compared to healthy males. The same adduct and 4-OHEI-2-NacCys were also detected at a much higher level in urine from a woman with breast carcinoma than samples from healthy controls. These two DNA adducts may serve as novel biomarkers for early diagnostic of cancers. The adsorption properties of R-phycoerythrin (RPE), on the fused-silica surface were studied using capillary electrophoresis (CE) and single molecule spectroscopy. The band shapes and migration times were measured in CE. Adsorption and desorption events were recorded at the single-molecule level by imaging of the evanescent-field layer using total internal reflection. The adsorbed RPE molecules on the fused-silica prism surface were

  1. Comparison of negative-ion proton-transfer with iodide ion chemical ionization mass spectrometry for quantification of isocyanic acid in ambient air

    NASA Astrophysics Data System (ADS)

    Woodward-Massey, Robert; Taha, Youssef M.; Moussa, Samar G.; Osthoff, Hans D.

    2014-12-01

    Isocyanic acid (HNCO) is a trace gas pollutant of potential importance to human health whose measurement has recently become possible through the development of negative-ion proton-transfer chemical ionization mass spectrometry (NI-PT-CIMS) with acetate reagent ion. In this manuscript, an alternative ionization and detection scheme, in which HNCO is quantified by iodide CIMS (iCIMS) as a cluster ion at m/z 170, is described. The sensitivity was inversely proportional to water vapor concentration but could be made independent of humidity changes in the sampled air by humidifying the ion-molecule reaction (IMR) region of the CIMS. The performance of the two ionization schemes was compared and contrasted using ambient air measurements of HNCO mixing ratios in Calgary, AB, Canada, by NI-PT-CIMS with acetate reagent ion from Dec 16 to 20, 2013, and by the same CIMS operated in iCIMS mode from Feb 3 to 7, 2014. The iCIMS exhibited a greater signal-to-noise ratio than the NI-PT-CIMS, not because of its sensitivity, which was lower (˜0.083 normalized counts per second (NCPS) per parts-per-trillion by volume (pptv) compared to ˜9.7 NCPS pptv-1), but because of a much lower and more stable background (3 ± 4 compared to a range of ˜2 × 103 to ˜6 × 103 NCPS). For the Feb 2014 data set, the HNCO mixing ratios in Calgary air ranged from <12 to 94 pptv (median 34 pptv), were marginally higher at night than during day, and correlated with nitrogen oxide (NOx = NO + NO2) mixing ratios and submicron particle volume. The ratios of HNCO to NOx observed are within the range of emission ratios reported for gasoline-powered motor vehicles.

  2. A new dynamical atmospheric ionizing radiation (AIR) model for epidemiological studies

    NASA Technical Reports Server (NTRS)

    De Angelis, G.; Clem, J. M.; Goldhagen, P. E.; Wilson, J. W.

    2003-01-01

    A new Atmospheric Ionizing Radiation (AIR) model is currently being developed for use in radiation dose evaluation in epidemiological studies targeted to atmospheric flight personnel such as civilian airlines crewmembers. The model will allow computing values for biologically relevant parameters, e.g. dose equivalent and effective dose, for individual flights from 1945. Each flight is described by its actual three dimensional flight profile, i.e. geographic coordinates and altitudes varying with time. Solar modulated primary particles are filtered with a new analytical fully angular dependent geomagnetic cut off rigidity model, as a function of latitude, longitude, arrival direction, altitude and time. The particle transport results have been obtained with a technique based on the three-dimensional Monte Carlo transport code FLUKA, with a special procedure to deal with HZE particles. Particle fluxes are transformed into dose-related quantities and then integrated all along the flight path to obtain the overall flight dose. Preliminary validations of the particle transport technique using data from the AIR Project ER-2 flight campaign of measurements are encouraging. Future efforts will deal with modeling of the effects of the aircraft structure as well as inclusion of solar particle events. Published by Elsevier Ltd on behalf of COSPAR.

  3. Nonperturbative time-dependent density-functional theory of ionization and harmonic generation in OCS and CS{sub 2} molecules with ultrashort intense laser pulses: Intensity and orientational effects

    SciTech Connect

    Penka Fowe, Emmanuel; Bandrauk, Andre D.

    2011-09-15

    Molecular high-order harmonic generation (MHOHG) and molecular orbital ionization rates are calculated for the nonsymmetric OCS and symmetric CS{sub 2} molecules using numerical solutions of Kohn-Sham (KS) equations of time-dependent density functional theory in the nonlinear nonperturbative regime of laser-molecule interactions for different laser-molecule orientations and intensities. It is found that the ionization of inner-shell KS molecular orbitals contributes significantly to the ionization and MHOHG processes for intensities I{>=} 3.5 x 10{sup 14} W/cm{sup 2}. Ionization rate maxima correspond to the alignment of maximum KS orbital densities with the laser pulse polarization instead of orbital ionization potentials. Furthermore, degeneracies of orbitals are removed as a function of laser-molecule angle, thus affecting ionization rates, the MHOHG spectra, and their polarizations, the latter allowing for identifying inner-orbital ionization.

  4. Calculations for ion-impact induced ionization and fragmentation of water molecules

    NASA Astrophysics Data System (ADS)

    Kirchner, Tom; Murakami, Mitsuko; Horbatsch, Marko; Jürgen Lüdde, Hans

    2012-10-01

    Charge-state correlated cross sections for single- and multiple-electron removal processes in proton-water-molecule collisions are calculated by using the non-perturbative basis generator method adapted for ion-molecule collisions [1,2]. A fragmentation model is then applied to calculate the yields of H2O^+, OH^+, H^+, and O^+ ions emerging after H2O^q+ formation [3]. A detailed comparison is made with experimental data from three groups covering the energy range from 20--5000 keV. It is found that multiple electron processes with q<=3 play an important role at the lower end of this range and are calculated accurately within an independent particle model. We are currently completing the analogous analysis for He^+-H2O collisions for which the presence of the projectile electron poses some additional challenges. [4pt] [1] H.J. L"udde et al, Phys. Rev. A 80, 060702(R) (2009)[0pt] [2] M. Murakami et al, Phys. Rev. A 85, 052704 (2012)[0pt] [3] M. Murakami et al, Phys. Rev. A 85, 052713 (2012)

  5. Radical Cationic Pathway for the Decay of Ionized Glyme Molecules in Liquid Solution.

    PubMed

    Taletskiy, Konstantin S; Borovkov, Vsevolod I; Schegoleva, Lyudmila N; Beregovaya, Irina V; Taratayko, Andrey I; Molin, Yuriy N

    2015-11-12

    Chemical stability of primary radical cations (RCs) generated in irradiated matter determines substantially the radiation resistance of organic materials. Transformations of the RCs of the glyme molecules, R(-O-CH2-CH2-)nO-R (R = CH3, n = 1-4) has been studied on the nanosecond time scale by measuring the magnetic field effects in the recombination fluorescence from irradiated liquid solutions of the glymes. In all cases, the RCs observed were different from that expected for the primary ones and revealed very similar hyperfine couplings independent of the poly(ethylene oxide) chain length and of the substitution of terminal methyl groups by C2H5 or CH2CH2Cl, as has been shown with diglyme as an example. Quantum chemical analysis of possible chemical transformations for the monoglyme RC as a model system allowed us to discover the reaction pathway yielding the methyl vinyl ether RC. The pathway involves intramolecular proton transfer followed by C-O bond cleavage. Only one (-O-CH2-CH2-O-) fragment is involved in this transformation, which is nearly barrierless due to the catalytic effect of adjacent glyme molecules. The rapid formation of the methyl vinyl ether RC in the irradiated monoglyme was confirmed by the numerical simulation of the experimental curves of the time-resolved magnetic field effect. These findings suggest that the R'-O-CH═CH2(•+) formation is a typical decay pathway for the primary RCs in irradiated liquid glymes. PMID:26472520

  6. Ionization of small molecules induced by H+, H e+ , and N+ projectiles: Comparison of experiment with quantum and classical calculations

    NASA Astrophysics Data System (ADS)

    Kovács, S. T. S.; Herczku, P.; Juhász, Z.; Sarkadi, L.; Gulyás, L.; Sulik, B.

    2016-07-01

    We report the energy and angular distribution of ejected electrons from C H4 and H2O molecules impacted by 1 MeV H+, H e+ , and 650 keV N+ ions. Spectra were measured at different observation angles, from 2 to 2000 eV. The obtained absolute double-differential electron-emission cross sections (DDCSs) were compared with the results of classical trajectory Monte Carlo (CTMC) and continuum distorted wave, eikonal initial state (CDW-EIS) calculations. For the bare H+ projectile both theories show remarkable agreement with the experiment at all observed angles and energies. The CTMC results are in similarly good agreement with the DDCS spectra obtained for impact by dressed H e+ and N+ ions, where screening effects and electron loss from the projectile gain importance. The CDW-EIS calculations slightly overestimate the electron loss for 1 MeV H e+ impact, and overestimate both the target and projectile ionization at low emitted electron energies for 650 keV N+ impact. The contribution of multiple electron scattering by the projectile and target centers (Fermi shuttle) dominates the N+-impact spectra at higher electron energies, and it is well reproduced by the nonperturbative CTMC calculations. The contributions of different processes in medium-velocity collisions of dressed ions with molecules are determined.

  7. X-ray multiphoton ionization dynamics of a water molecule irradiated by an x-ray free-electron laser pulse

    NASA Astrophysics Data System (ADS)

    Inhester, Ludger; Hanasaki, Kota; Hao, Yajiang; Son, Sang-Kil; Santra, Robin

    2016-08-01

    We present a theoretical investigation of x-ray multiphoton ionization dynamics of polyatomic molecules, based on the rate equation model and molecular electronic structure calculations. An efficient numerical procedure is developed to calculate photoionization cross sections, Auger rates, and fluorescence rates for all possible electronic multiple-hole configurations of molecules. We investigate the charge-state distribution of a water molecule after interaction with an intense x-ray pulse and discuss its dependence on the fluence and the pulse duration of the x-ray beam. Our results demonstrate that a water molecule exposed to an intense x-ray pulse is more ionized than what would be expected within the independent-atom picture.

  8. Charge and Nuclear Dynamics Induced by Deep Inner-Shell Multiphoton Ionization of CH3I Molecules by Intense X-ray Free-Electron Laser Pulses.

    PubMed

    Motomura, Koji; Kukk, Edwin; Fukuzawa, Hironobu; Wada, Shin-ichi; Nagaya, Kiyonobu; Ohmura, Satoshi; Mondal, Subhendu; Tachibana, Tetsuya; Ito, Yuta; Koga, Ryosuke; Sakai, Tsukasa; Matsunami, Kenji; Rudenko, Artem; Nicolas, Christophe; Liu, Xiao-Jing; Miron, Catalin; Zhang, Yizhu; Jiang, Yuhai; Chen, Jianhui; Anand, Mailam; Kim, Dong Eon; Tono, Kensuke; Yabashi, Makina; Yao, Makoto; Ueda, Kiyoshi

    2015-08-01

    In recent years, free-electron lasers operating in the true X-ray regime have opened up access to the femtosecond-scale dynamics induced by deep inner-shell ionization. We have investigated charge creation and transfer dynamics in the context of molecular Coulomb explosion of a single molecule, exposed to sequential deep inner-shell ionization within an ultrashort (10 fs) X-ray pulse. The target molecule was CH3I, methane sensitized to X-rays by halogenization with a heavy element, iodine. Time-of-flight ion spectroscopy and coincident ion analysis was employed to investigate, via the properties of the atomic fragments, single-molecule charge states of up to +22. Experimental findings have been compared with a parametric model of simultaneous Coulomb explosion and charge transfer in the molecule. The study demonstrates that including realistic charge dynamics is imperative when molecular Coulomb explosion experiments using short-pulse facilities are performed.

  9. Double-ionization energies of some n-alkyl isocyanate molecules; studies with double-charge-transfer spectrometry and ab initio propagator theory

    NASA Astrophysics Data System (ADS)

    Bayliss, M. A.; Griffiths, I. W.; Harris, F. M.; Parry, D. E.

    2003-12-01

    Double-charge-transfer (DCT) collisions of H+, OH+ and F+ 3 keV beam ions with a series of alkyl isocyanate molecules were studied using mass spectrometric techniques. Measurement of the kinetic energies of H- ions so produced enabled the determination of double-ionization energies (DIE) for transitions to singlet doubly ionized states of the target molecules; those for triplet doubly ionized states were obtained similarly from measurements of the kinetic energies of OH- and F- ions. Values up to approximately 40 eV were obtained in most cases and were found to be in close agreement with the predictions of ab initio calculations using propagator theory, also presented here. For n-butyl isocyanate (and by implication heavier molecules in the series) the density of doubly ionized states above 30 eV was both observed and predicted to be too large and featureless for meaningful analysis, so establishing an effective upper limit on molecular size for the current application of these techniques. Significant configuration interaction was predicted for the final doubly ionized states, which justified theoretical analysis with a relatively complex method that accounts well for correlation effects.

  10. Evaluating the Translational Temperature of Molecules Laser-desorbed after Online Concentration Using Multiphoton Ionization Time-of-Flight Mass Spectrometry.

    PubMed

    Miura, Shuhei; Uchimura, Tomohiro

    2016-01-01

    We describe a new technique for evaluating the translational temperature of molecules by applying online concentration via analyte adsorption/laser desorption, which is a sample-introduction technique for resonance-enhanced multiphoton ionization time-of-flight mass spectrometry (REMPI-TOFMS). In the present study, analyte molecules were adsorbed via a narrowed capillary tip once, and then the flow of the carrier gas containing the analyte was stopped. After laser desorption, the ion signals induced by REMPI were monitored. Finally, the translational temperature could be calculated from the velocity distribution of the desorbed molecules by applying a Maxwell distribution. PMID:27682410

  11. Molecular Threading: Mechanical Extraction, Stretching and Placement of DNA Molecules from a Liquid-Air Interface

    PubMed Central

    Kemmish, Kent; Hamalainen, Mark; Bowell, Charlotte; Bleloch, Andrew; Klejwa, Nathan; Lehrach, Wolfgang; Schatz, Ken; Stark, Heather; Marblestone, Adam; Church, George; Own, Christopher S.; Andregg, William

    2013-01-01

    We present “molecular threading”, a surface independent tip-based method for stretching and depositing single and double-stranded DNA molecules. DNA is stretched into air at a liquid-air interface, and can be subsequently deposited onto a dry substrate isolated from solution. The design of an apparatus used for molecular threading is presented, and fluorescence and electron microscopies are used to characterize the angular distribution, straightness, and reproducibility of stretched DNA deposited in arrays onto elastomeric surfaces and thin membranes. Molecular threading demonstrates high straightness and uniformity over length scales from nanometers to micrometers, and represents an alternative to existing DNA deposition and linearization methods. These results point towards scalable and high-throughput precision manipulation of single-molecule polymers. PMID:23935923

  12. Dust particle charge screening in the dry-air plasma produced by an external ionization source

    SciTech Connect

    Derbenev, I. N.; Filippov, A. V.

    2015-08-15

    The ionic composition of the plasma produced by an external ionization source in dry air at atmospheric pressure and room temperature and the screening of the electric field of a dust particle in such a plasma have been investigated. The point sink model based on the diffusion-drift approximation has been used to solve the screening problem. We have established that the main species of ions in the plasma under consideration are O{sub 4}{sup +}, O{sub 2}{sup -}, and O{sub 4}{sup -} and that the dust particle potential distribution is described by a superposition of four exponentials with four different constants. We show that the first constant coincides with the inverse Debye length, the second is described by the inverse ambipolar diffusion length of the positive and negative plasma components in the characteristic time of their recombination, the third is determined by the conversion of negative ions, and the fourth is determined by the attachment and recombination of electrons and diatomic ions.

  13. Metronomic Small Molecule Inhibitor of Bcl-2 (TW-37) Is Antiangiogenic and Potentiates the Antitumor Effect of Ionizing Radiation

    SciTech Connect

    Zeitlin, Benjamin D.; Spalding, Aaron C.; Campos, Marcia S.; Ashimori, Naoki; Dong Zhihong; Wang Shaomeng; Lawrence, Theodore S.; Noer, Jacques E.

    2010-11-01

    Purpose: To investigate the effect of a metronomic (low-dose, high-frequency) small-molecule inhibitor of Bcl-2 (TW-37) in combination with radiotherapy on microvascular endothelial cells in vitro and in tumor angiogenesis in vivo. Methods and Materials: Primary human dermal microvascular endothelial cells were exposed to ionizing radiation and/or TW-37 and colony formation, as well as capillary sprouting in three-dimensional collagen matrices, was evaluated. Xenografts vascularized with human blood vessels were engineered by cotransplantation of human squamous cell carcinoma cells (OSCC3) and human dermal microvascular endothelial cells seeded in highly porous biodegradable scaffolds into the subcutaneous space of immunodeficient mice. Mice were treated with metronomic TW-37 and/or radiation, and tumor growth was evaluated. Results: Low-dose TW-37 sensitized primary endothelial cells to radiation-induced inhibition of colony formation. Low-dose TW-37 or radiation partially inhibited endothelial cell sprout formation, and in combination, these therapies abrogated new sprouting. Combination of metronomic TW-37 and low-dose radiation inhibited tumor growth and resulted in significant increase in time to failure compared with controls, whereas single agents did not. Notably, histopathologic analysis revealed that tumors treated with TW-37 (with or without radiation) are more differentiated and showed more cohesive invasive fronts, which is consistent with less aggressive phenotype. Conclusions: These results demonstrate that metronomic TW-37 potentiates the antitumor effects of radiotherapy and suggest that patients with head and neck cancer might benefit from the combination of small molecule inhibitor of Bcl-2 and radiation therapy.

  14. N1s and O1s double ionization of the NO and N{sub 2}O molecules

    SciTech Connect

    Hedin, L.; Zhaunerchyk, V.; Karlsson, L.; Pernestål, K.; Feifel, R.; Tashiro, M.; Ehara, M.; Linusson, P.; Eland, J. H. D.; Ueda, K.

    2014-01-28

    Single-site N1s and O1s double core ionisation of the NO and N{sub 2}O molecules has been studied using a magnetic bottle many-electron coincidence time-of-flight spectrometer at photon energies of 1100 eV and 1300 eV. The double core hole energies obtained for NO are 904.8 eV (N1s{sup −2}) and 1179.4 eV (O1s{sup −2}). The corresponding energies obtained for N{sub 2}O are 896.9 eV (terminal N1s{sup −2}), 906.5 eV (central N1s{sup −2}), and 1174.1 eV (O1s{sup −2}). The ratio between the double and single ionisation energies are in all cases close or equal to 2.20. Large chemical shifts are observed in some cases which suggest that reorganisation of the electrons upon the double ionization is significant. Δ-self-consistent field and complete active space self-consistent field (CASSCF) calculations were performed for both molecules and they are in good agreement with these results. Auger spectra of N{sub 2}O, associated with the decay of the terminal and central N1s{sup −2} as well as with the O1s{sup −2} dicationic states, were extracted showing the two electrons emitted as a result of filling the double core holes. The spectra, which are interpreted using CASSCF and complete active space configuration interaction calculations, show atomic-like character. The cross section ratio between double and single core hole creation was estimated as 1.6 × 10{sup −3} for nitrogen at 1100 eV and as 1.3 × 10{sup −3} for oxygen at 1300 eV.

  15. Screening of the binding of small molecules to proteins by desorption electrospray ionization mass spectrometry combined with protein microarray.

    PubMed

    Yao, Chenxi; Wang, Tao; Zhang, Buqing; He, Dacheng; Na, Na; Ouyang, Jin

    2015-11-01

    The interaction between bioactive small molecule ligands and proteins is one of the important research areas in proteomics. Herein, a simple and rapid method is established to screen small ligands that bind to proteins. We designed an agarose slide to immobilize different proteins. The protein microarrays were allowed to interact with different small ligands, and after washing, the microarrays were screened by desorption electrospray ionization mass spectrometry (DESI MS). This method can be applied to screen specific protein binding ligands and was shown for seven proteins and 34 known ligands for these proteins. In addition, a high-throughput screening was achieved, with the analysis requiring approximately 4 s for one sample spot. We then applied this method to determine the binding between the important protein matrix metalloproteinase-9 (MMP-9) and 88 small compounds. The molecular docking results confirmed the MS results, demonstrating that this method is suitable for the rapid and accurate screening of ligands binding to proteins. Graphical Abstract ᅟ. PMID:26174365

  16. Screening of the binding of small molecules to proteins by desorption electrospray ionization mass spectrometry combined with protein microarray.

    PubMed

    Yao, Chenxi; Wang, Tao; Zhang, Buqing; He, Dacheng; Na, Na; Ouyang, Jin

    2015-11-01

    The interaction between bioactive small molecule ligands and proteins is one of the important research areas in proteomics. Herein, a simple and rapid method is established to screen small ligands that bind to proteins. We designed an agarose slide to immobilize different proteins. The protein microarrays were allowed to interact with different small ligands, and after washing, the microarrays were screened by desorption electrospray ionization mass spectrometry (DESI MS). This method can be applied to screen specific protein binding ligands and was shown for seven proteins and 34 known ligands for these proteins. In addition, a high-throughput screening was achieved, with the analysis requiring approximately 4 s for one sample spot. We then applied this method to determine the binding between the important protein matrix metalloproteinase-9 (MMP-9) and 88 small compounds. The molecular docking results confirmed the MS results, demonstrating that this method is suitable for the rapid and accurate screening of ligands binding to proteins. Graphical Abstract ᅟ.

  17. Investigations of the potential functions of weakly bound diatomic molecules and laser-assisted excitive Penning ionization

    SciTech Connect

    Goble, J.H. Jr.

    1982-05-01

    Three variations on the Dunham series expansion function of the potential of a diatomic molecule are compared. The differences among these expansions lie in the choice of the expansion variable, lambda. The functional form of these variables are lambda/sub s/ = l-r/sub e//r for the Simon-Parr-Finlan version, lambda/sub T/ - 1-(r/sub e//r)/sup p/ for that of Thakkar, and lambda/sub H/ = 1-exp(-rho(r/r/sub e/-1) for that of Huffaker. A wide selection of molecular systems are examined. It is found that, for potentials in excess of thirty kcal/mole, the Huffaker expansion provides the best description of the three, extrapolating at large internuclear separation to a value within 10% of the true dissociation energy. For potentials that result from the interaction of excited states, all series expansions show poor behavior away from the equilibrium internuclear separation of the molecule. The series representation of the potentials of weakly bound molecules are examined in more detail. The ground states of BeAr/sup +/, HeNe/sup +/, NaAr, and Ar/sub 2/ and the excited states of HeNe+, NaNe, and NaAr are best described by the Thakkar expansion. Finally, the observation of laser-assisted excitive Penning ionization in a flowing afterglow is reported. The reaction Ar(/sup 3/P/sub 2/) + Ca + h nu ..-->.. Ar + Ca/sup +/(5p /sup 2/P/sub J/) + e/sup -/ occurs when the photon energy, h nu, is approximately equal to the energy difference between the metastable argon and one of the fine structure levels of the ion's doublet. By monitoring the cascade fluorescence of the above reaction and comparing it to the flourescence from the field-free process Ar(/sup 3/P/sub 2/) + Ca ..-->.. Ar + Ca/sup +/(4p /sup 2/P/sub J/) + e/sup -/ a surprisingly large cross section of 6.7 x 10/sup 3/ A/sup 2/ is estimated.

  18. Monte Carlo Simulation in the Optimization of a Free-Air Ionization Chamber for Dosimetric Control in Medical Digital Radiography

    NASA Astrophysics Data System (ADS)

    Leyva, A.; Piñera, I.; Montaño, L. M.; Abreu, Y.; Cruz, C. M.

    2008-08-01

    During the earliest tests of a free-air ionization chamber a poor response to the X-rays emitted by several sources was observed. Then, the Monte Carlo simulation of X-rays transport in matter was employed in order to evaluate chamber behavior as X-rays detector. The photons energy deposition dependence with depth and its integral value in all active volume were calculated. The obtained results reveal that the designed device geometry is feasible to be optimized.

  19. Electron Transport Coefficients and Effective Ionization Coefficients in SF6-O2 and SF6-Air Mixtures Using Boltzmann Analysis

    NASA Astrophysics Data System (ADS)

    Wei, Linsheng; Xu, Min; Yuan, Dingkun; Zhang, Yafang; Hu, Zhaoji; Tan, Zhihong

    2014-10-01

    The electron drift velocity, electron energy distribution function (EEDF), density-normalized effective ionization coefficient and density-normalized longitudinal diffusion velocity are calculated in SF6-O2 and SF6-Air mixtures. The experimental results from a pulsed Townsend discharge are plotted for comparison with the numerical results. The reduced field strength varies from 40 Td to 500 Td (1 Townsend=10-17 V·cm2) and the SF6 concentration ranges from 10% to 100%. A Boltzmann equation associated with the two-term spherical harmonic expansion approximation is utilized to gain the swarm parameters in steady-state Townsend. Results show that the accuracy of the Boltzmann solution with a two-term expansion in calculating the electron drift velocity, electron energy distribution function, and density-normalized effective ionization coefficient is acceptable. The effective ionization coefficient presents a distinct relationship with the SF6 content in the mixtures. Moreover, the E/Ncr values in SF6-Air mixtures are higher than those in SF6-O2 mixtures and the calculated value E/Ncr in SF6-O2 and SF6-Air mixtures is lower than the measured value in SF6-N2. Parametric studies conducted on these parameters using the Boltzmann analysis offer substantial insight into the plasma physics, as well as a basis to explore the ozone generation process.

  20. Carbon Dots and 9AA as a Binary Matrix for the Detection of Small Molecules by Matrix-Assisted Laser Desorption/Ionization Mass Spectrometry.

    PubMed

    Chen, Yongli; Gao, Dan; Bai, Hangrui; Liu, Hongxia; Lin, Shuo; Jiang, Yuyang

    2016-07-01

    Application of matrix-assisted laser-desorption/ionization mass spectrometry (MALDI MS) to analyze small molecules have some limitations, due to the inhomogeneous analyte/matrix co-crystallization and interference of matrix-related peaks in low m/z region. In this work, carbon dots (CDs) were for the first time applied as a binary matrix with 9-Aminoacridine (9AA) in MALDI MS for small molecules analysis. By 9AA/CDs assisted desorption/ionization (D/I) process, a wide range of small molecules, including nucleosides, amino acids, oligosaccharides, peptides, and anticancer drugs with a higher sensitivity were demonstrated in the positive ion mode. A detection limit down to 5 fmol was achieved for cytidine. 9AA/CDs matrix also exhibited excellent reproducibility compared with 9AA matrix. Moreover, by exploring the ionization mechanism of the matrix, the influence factors might be attributed to the four parts: (1) the strong UV absorption of 9AA/CDs due to their π-conjugated network; (2) the carboxyl groups modified on the CDs surface act as protonation sites for proton transfer in positive ion mode; (3) the thin layer crystal of 9AA/CDs could reach a high surface temperature more easily and lower transfer energy for LDI MS; (4) CDs could serve as a matrix additive to suppress 9AA ionization. Furthermore, this matrix was allowed for the analysis of glucose as well as nucleosides in human urine, and the level of cytidine was quantified with a linear range of 0.05-5 mM (R(2) > 0.99). Therefore, the 9AA/CDs matrix was proven to be an effective MALDI matrix for the analysis of small molecules with improved sensitivity and reproducibility. This work provides an alternative solution for small molecules detection that can be further used in complex samples analysis. Graphical Abstract ᅟ.

  1. Carbon Dots and 9AA as a Binary Matrix for the Detection of Small Molecules by Matrix-Assisted Laser Desorption/Ionization Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Chen, Yongli; Gao, Dan; Bai, Hangrui; Liu, Hongxia; Lin, Shuo; Jiang, Yuyang

    2016-07-01

    Application of matrix-assisted laser-desorption/ionization mass spectrometry (MALDI MS) to analyze small molecules have some limitations, due to the inhomogeneous analyte/matrix co-crystallization and interference of matrix-related peaks in low m/z region. In this work, carbon dots (CDs) were for the first time applied as a binary matrix with 9-Aminoacridine (9AA) in MALDI MS for small molecules analysis. By 9AA/CDs assisted desorption/ionization (D/I) process, a wide range of small molecules, including nucleosides, amino acids, oligosaccharides, peptides, and anticancer drugs with a higher sensitivity were demonstrated in the positive ion mode. A detection limit down to 5 fmol was achieved for cytidine. 9AA/CDs matrix also exhibited excellent reproducibility compared with 9AA matrix. Moreover, by exploring the ionization mechanism of the matrix, the influence factors might be attributed to the four parts: (1) the strong UV absorption of 9AA/CDs due to their π-conjugated network; (2) the carboxyl groups modified on the CDs surface act as protonation sites for proton transfer in positive ion mode; (3) the thin layer crystal of 9AA/CDs could reach a high surface temperature more easily and lower transfer energy for LDI MS; (4) CDs could serve as a matrix additive to suppress 9AA ionization. Furthermore, this matrix was allowed for the analysis of glucose as well as nucleosides in human urine, and the level of cytidine was quantified with a linear range of 0.05-5 mM (R2 > 0.99). Therefore, the 9AA/CDs matrix was proven to be an effective MALDI matrix for the analysis of small molecules with improved sensitivity and reproducibility. This work provides an alternative solution for small molecules detection that can be further used in complex samples analysis.

  2. Dependence with air density of the response of the PTW SourceCheck ionization chamber for low energy brachytherapy sources

    SciTech Connect

    Tornero-López, Ana M.; Guirado, Damián; Ruiz-Arrebola, Samuel; Perez-Calatayud, Jose; Simancas, Fernando; Lallena, Antonio M.; Gazdic-Santic, Maja

    2013-12-15

    Purpose: Air-communicating well ionization chambers are commonly used to assess air kerma strength of sources used in brachytherapy. The signal produced is supposed to be proportional to the air density within the chamber and, therefore, a density-independent air kerma strength is obtained when the measurement is corrected to standard atmospheric conditions using the usual temperature and pressure correction factor. Nevertheless, when assessing low energy sources, the ionization chambers may not fulfill that condition and a residual density dependence still remains after correction. In this work, the authors examined the behavior of the PTW 34051 SourceCheck ionization chamber when measuring the air kerma strength of {sup 125}I seeds.Methods: Four different SourceCheck chambers were analyzed. With each one of them, two series of measurements of the air kerma strength for {sup 125}I selectSeed{sup TM} brachytherapy sources were performed inside a pressure chamber and varying the pressure in a range from 747 to 1040 hPa (560 to 780 mm Hg). The temperature and relative humidity were kept basically constant. An analogous experiment was performed by taking measurements at different altitudes above sea level.Results: Contrary to other well-known ionization chambers, like the HDR1000 PLUS, in which the temperature-pressure correction factor overcorrects the measurements, in the SourceCheck ionization chamber they are undercorrected. At a typical atmospheric situation of 933 hPa (700 mm Hg) and 20 °C, this undercorrection turns out to be 1.5%. Corrected measurements show a residual linear dependence on the density and, as a consequence, an additional density dependent correction must be applied. The slope of this residual linear density dependence is different for each SourceCheck chamber investigated. The results obtained by taking measurements at different altitudes are compatible with those obtained with the pressure chamber.Conclusions: Variations of the altitude and

  3. Two-center interference effects on the orientation dependence of the strong-field double-ionization yields for hydrogen molecules

    NASA Astrophysics Data System (ADS)

    Li, W.; Liu, J.

    2012-09-01

    In the present paper we investigate the orientation dependence of the nonsequential double ionization (NSDI) of a hydrogen molecule (H2) exposed to a strong laser field analytically within the strong-field approximation. Our calculations demonstrate that the NSDI yields can increase with the increase of the molecular alignment angle; i.e., the alignment dependence of the NSDI yields exhibit a reversed tendency compared to that of the single-ionization yields. This striking phenomenon is identified as a signal of quantum interference, which arises from the two-center structure of the diatomic molecule and can lead to the dramatic suppression of the NSDI rates at small alignment angles. Moreover, the interference effect can be altered by both laser intensity and internuclear distance. The above finding indicates that the two-center interference can affect NSDI yields dramatically in certain cases and therefore suggests a feasible way to observe the interference effect indirectly in NSDI experiments.

  4. Theoretical study of orientation-dependent multiphoton ionization of polyatomic molecules in intense ultrashort laser fields: A new time-dependent Voronoi-cell finite difference method

    NASA Astrophysics Data System (ADS)

    Son, Sang-Kil; Chu, Shih-I.

    2009-12-01

    We present a new grid-based time-dependent method to investigate multiphoton ionization (MPI) of polyatomic molecules in intense ultrashort laser fields. The electronic structure of polyatomic molecules is treated by the density-functional theory (DFT) with proper long-range potential and the Kohn-Sham equation is accurately solved by means of the Voronoi-cell finite difference method on non-uniform and highly adaptive molecular grids utilizing geometrical flexibility of the Voronoi diagram. This method is generalized to the time-dependent problems with the split-operator time-propagation technique in the energy representation, allowing accurate and efficient non-perturbative treatment of attosecond electronic dynamics in strong fields. The new procedure is applied to the study of MPI of N 2 and H 2O molecules in intense linearly-polarized and ultrashort laser fields with arbitrary field-molecule orientation. Our results demonstrate that the orientation dependence of MPI is determined not just by the highest-occupied molecular orbital (HOMO) but also by the symmetries and dynamics of other contributing molecular orbitals. In particular, the inner orbitals can show dominant contributions to the ionization processes when the molecule is aligned in some specific directions with respect to the field polarization. This feature suggests a new way to selectively probe individual orbitals in strong-field electronic dynamics.

  5. Constraining the sensitivity of iodide adduct chemical ionization mass spectrometry to multifunctional organic molecules using the collision limit and thermodynamic stability of iodide ion adducts

    DOE PAGES

    Lopez-Hilfiker, Felipe D.; Iyer, Siddarth; Mohr, Claudia; Lee, Ben H.; D'Ambro, Emma L.; Kurtén, Theo; Thornton, Joel A.

    2016-04-06

    The sensitivity of a chemical ionization mass spectrometer (ions formed per number density of analytes) is fundamentally limited by the collision frequency between reagent ions and analytes, known as the collision limit, the ion–molecule reaction time, and the transmission efficiency of product ions to the detector. We use the response of a time-of-flight chemical ionization mass spectrometer (ToF-CIMS) to N2O5, known to react with iodide at the collision limit, to constrain the combined effects of ion–molecule reaction time, which is strongly influenced by mixing and ion losses in the ion–molecule reaction drift tube. A mass spectrometric voltage scanning procedure elucidatesmore » the relative binding energies of the ion adducts, which influence the transmission efficiency of molecular ions through the electric fields within the vacuum chamber. Together, this information provides a critical constraint on the sensitivity of a ToF-CIMS towards a wide suite of routinely detected multifunctional organic molecules for which no calibration standards exist. We describe the scanning procedure and collision limit determination, and we show results from the application of these constraints to the measurement of organic aerosol composition at two different field locations.« less

  6. Constraining the sensitivity of iodide adduct chemical ionization mass spectrometry to multifunctional organic molecules using the collision limit and thermodynamic stability of iodide ion adducts

    NASA Astrophysics Data System (ADS)

    Lopez-Hilfiker, Felipe D.; Iyer, Siddarth; Mohr, Claudia; Lee, Ben H.; D'Ambro, Emma L.; Kurtén, Theo; Thornton, Joel A.

    2016-04-01

    The sensitivity of a chemical ionization mass spectrometer (ions formed per number density of analytes) is fundamentally limited by the collision frequency between reagent ions and analytes, known as the collision limit, the ion-molecule reaction time, and the transmission efficiency of product ions to the detector. We use the response of a time-of-flight chemical ionization mass spectrometer (ToF-CIMS) to N2O5, known to react with iodide at the collision limit, to constrain the combined effects of ion-molecule reaction time, which is strongly influenced by mixing and ion losses in the ion-molecule reaction drift tube. A mass spectrometric voltage scanning procedure elucidates the relative binding energies of the ion adducts, which influence the transmission efficiency of molecular ions through the electric fields within the vacuum chamber. Together, this information provides a critical constraint on the sensitivity of a ToF-CIMS towards a wide suite of routinely detected multifunctional organic molecules for which no calibration standards exist. We describe the scanning procedure and collision limit determination, and we show results from the application of these constraints to the measurement of organic aerosol composition at two different field locations.

  7. Tailor-Made Stable Zr(IV)-Based Metal-Organic Frameworks for Laser Desorption/Ionization Mass Spectrometry Analysis of Small Molecules and Simultaneous Enrichment of Phosphopeptides.

    PubMed

    Chen, Lianfang; Ou, Junjie; Wang, Hongwei; Liu, Zhongshan; Ye, Mingliang; Zou, Hanfa

    2016-08-10

    Although thousands of metal-organic frameworks (MOFs) have been fabricated and widely applied in gas storage/separations, adsorption, catalysis, and so on, few kinds of MOFs have been used as adsorption materials while simultaneously serving as matrixes to analyze small molecules for laser desorption/ionization mass spectrometry (LDI-MS). Herein, a new concept is introduced to design and synthesize MOFs as both adsorption materials and matrixes according to the structure of ligands and common matrixes. The proof of concept design was demonstrated by selection of 2,5-pyridinedicarboxylic acid (PDC) and 2,5-dihydroxyterephthalic acid (DHT) as ligands for synthesis of MOFs. Two Zr(IV)-based MOFs of UiO-66-PDC and UiO-66-(OH)2 were synthesized and applied for the first time as new matrixes for analysis of small molecules by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS). Both of them showed low matrix interferences, high ionization efficiency, and good reproducibility when used as matrixes. A variety of small molecules, including saccharides, amino acids, nucleosides, peptides, alkaline drugs, and natural products, were analyzed. In addition, UiO-66-(OH)2 exhibited potential for application in the quantitative determination of glucose and pyridoxal 5'-phosphate. Furthermore, thanks to its intrinsically large surface area and highly ordered pores, UiO-66-(OH)2 also showed sensitive and specific enrichment of phosphopeptides prior to MS analysis. These results demonstrated that this strategy can be used to efficiently screen tailor-made MOFs as matrixes to analyze small molecules by MALDI-TOF-MS. PMID:27427857

  8. Colloidal Graphite-Assisted Laser Desorption/Ionization MS and MSn of Small Molecules. 2. Direct Profiling and MS Imaging of Small Metabolites from Fruits

    SciTech Connect

    Hui Zhang; Sangwon Cha; Edward S. Yeung

    2007-09-01

    Due to a high background in the low-mass region, conventional MALDI is not as useful for detecting small molecules (molecular masses <500 Da) as it is for large ones. Also, spatial inhomogeneity that is inherent to crystalline matrixes can degrade resolution in imaging mass spectrometry (IMS). In this study, colloidal graphite was investigated as an alternative matrix for laser desorption/ionization (GALDI) in IMS. We demonstrate its advantages over conventional MALDI in the detection of small molecules such as organic acids, flavonoids, and oligosaccharides. GALDI provides good sensitivity for such small molecules. The detection limit of fatty acids and flavonoids in the negative-ion mode are in the low-femtomole range. Molecules were detected directly and identified by comparing the MS and MS/MS spectra with those of standards. Various fruits were chosen to evaluate the practical utility of GALDI since many types of small molecules are present in them. Distribution of these small molecules in the fruit was investigated by using IMS and IMS/MS.

  9. Ionizer assisted air filtration for collection of submicron and ultrafine particles-evaluation of long-term performance and influencing factors.

    PubMed

    Shi, Bingbing; Ekberg, Lars

    2015-06-01

    Previous research has demonstrated that unipolar ionization can enhance the filter performance to collect airborne particles, aeroallergens, and airborne microorganisms, without affecting the filter pressure drop. However, there is a lack of research on the long-term system performance as well as the influence of environmental and operational parameters. In this paper, both field and laboratory tests were carried out to evaluate the long-term particle collection efficiency of a synthetic filter of class M6 with and without ionization. The effect of air velocity, temperature, relative humidity, and particle concentration were further investigated in laboratory tests. Results showed that ionization enhanced the filtration efficiency by 40%-units during most of the operation time. When the ionization system was managed by periodically switching the ionizer polarity, the filtration efficiency against PM0.3-0.5 was maintained above 50% during half a year. Furthermore, the pressure drop of the ionizer-assisted M6 filter was 25-30% lower than that of a filter of class F7. The evaluation of various influencing factors demonstrated that (1) air moisture reduced the increase of filtration efficiency; (2) higher upstream particle concentration and air velocity decreased the filtration efficiency; and (3) the air temperature had very limited effect on the filtration efficiency.

  10. Resonance-enhanced multiphoton ionization of van der Waals molecules: Studies of spectroscopic shifts of phenyl acetylene clustered with molecules and atoms

    NASA Astrophysics Data System (ADS)

    Dao, P. D.; Morgan, S.; Castleman, A. W., Jr.

    1984-10-01

    Van der Waals molecules comprised of phenyl acetylene (PA) clustered with rare-gas atoms, R (R = Ne, Ar, Kr, Xe) and other molecules, M (M = N 2, O 2, N 2O, CO 2), H 2O, CCl 4, and NH 3) were formed via adiabatic expansion from a pulsed nozzle, subjected to resonance-erhanced MPI, and analyzed in a time-of-flight mass spectrometer. Studies of the perturbed L b( 1B 2) states reveal spectral shifts with respect to the aromatic molecule monomer. In the case of the rare-gas atoms the shift in frequency, which is red, linearly increases with the polarizability of the atom. Red-shifts were also seen for all other molecules except CO 2 and H 2O, where an appreciable blue-shift was observed in the case of the latter.

  11. In-Line Ozonation for Sensitive Air-Monitoring of a Mustard-Gas Simulant by Atmospheric Pressure Chemical Ionization Mass Spectrometry.

    PubMed

    Okumura, Akihiko

    2015-09-01

    A highly sensitive method for real-time air-monitoring of mustard gas (bis(2-chloroethyl) sulfide, HD), which is a lethal blister agent, is proposed. Humidified air containing a HD simulant, 2-chloroethyl ethyl sulfide (2CEES), was mixed with ozone and then analyzed by using an atmospheric pressure chemical ionization ion trap tandem mass spectrometer. Mass-spectral ion peaks attributable to protonated molecules of intact, monooxygenated, and dioxygenated 2CEES (MH(+), MOH(+), and MO(2)H(+), respectively) were observed. As ozone concentration was increased from zero to 30 ppm, the signal intensity of MH(+) sharply decreased, that of MOH(+) increased once and then decreased, and that of MO(2)H(+) sharply increased until reaching a plateau. The signal intensity of MO(2)H(+) at the plateau was 40 times higher than that of MH(+) and 100 times higher than that of MOH(+) in the case without in-line ozonation. Twenty-ppm ozone gas was adequate to give a linear calibration curve for 2CEES obtained by detecting the MO(2)H(+) signal in the concentration range up to 60 μg/m(3), which is high enough for hygiene management. In the low concentration range lower than 3 μg/m(3), which is equal to the short-term exposure limit for HD, calibration plots unexpectedly fell off the linear calibration curve, but 0.6-μg/m(3) vapor was actually detected with the signal-to-noise ratio of nine. Ozone was generated from instrumentation air by using a simple and inexpensive home-made generator. 2CEES was ozonated in 1-m extended sampling tube in only 1 s.

  12. In-Line Ozonation for Sensitive Air-Monitoring of a Mustard-Gas Simulant by Atmospheric Pressure Chemical Ionization Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Okumura, Akihiko

    2015-09-01

    A highly sensitive method for real-time air-monitoring of mustard gas (bis(2-chloroethyl) sulfide, HD), which is a lethal blister agent, is proposed. Humidified air containing a HD simulant, 2-chloroethyl ethyl sulfide (2CEES), was mixed with ozone and then analyzed by using an atmospheric pressure chemical ionization ion trap tandem mass spectrometer. Mass-spectral ion peaks attributable to protonated molecules of intact, monooxygenated, and dioxygenated 2CEES (MH+, MOH+, and MO2H+, respectively) were observed. As ozone concentration was increased from zero to 30 ppm, the signal intensity of MH+ sharply decreased, that of MOH+ increased once and then decreased, and that of MO2H+ sharply increased until reaching a plateau. The signal intensity of MO2H+ at the plateau was 40 times higher than that of MH+ and 100 times higher than that of MOH+ in the case without in-line ozonation. Twenty-ppm ozone gas was adequate to give a linear calibration curve for 2CEES obtained by detecting the MO2H+ signal in the concentration range up to 60 μg/m3, which is high enough for hygiene management. In the low concentration range lower than 3 μg/m3, which is equal to the short-term exposure limit for HD, calibration plots unexpectedly fell off the linear calibration curve, but 0.6-μg/m3 vapor was actually detected with the signal-to-noise ratio of nine. Ozone was generated from instrumentation air by using a simple and inexpensive home-made generator. 2CEES was ozonated in 1-m extended sampling tube in only 1 s.

  13. Experimental investigation of the effect of air cavity size in cylindrical ionization chambers on the measurements in ⁶⁰Co radiotherapy beams.

    PubMed

    Swanpalmer, John; Johansson, Karl-Axel

    2011-11-21

    In the late 1970s, Johansson et al (1978 Int. Symp. National and International Standardization of Radiation Dosimetry (Atlanta 1977) vol 2 (Vienna: IAEA) pp 243-70) reported experimentally determined displacement correction factors (p(dis)) for cylindrical ionization chamber dosimetry in ⁶⁰Co and high-energy photon beams. These p(dis) factors have been implemented and are currently in use in a number of dosimetry protocols. However, the accuracy of these factors has recently been questioned by Wang and Rogers (2009a Phys. Med. Biol. 54 1609-20), who performed Monte Carlo simulations of the experiments performed by Johansson et al. They reported that the inaccuracy of the p(dis) factors originated from the normalization procedure used by Johansson et al. In their experiments, Johansson et al normalized the measured depth-ionization curves at the depth of maximum ionization for each of the different ionization chambers. In this study, we experimentally investigated the effect of air cavity size of cylindrical ionization chambers in a PMMA phantom and ⁶⁰Co γ-beam. Two different pairs of air-filled cylindrical ionization chambers were used. The chambers in each pair had identical construction and materials but different air cavity volume (diameter). A 20 MeV electron beam was utilized to determine the ratio of the mass of air in the cavity of the two chambers in each pair. This ratio of the mass of air in each pair was then used to compare the ratios of the ionizations obtained at different depths in the PMMA phantom and ⁶⁰Co γ-beam using the two pairs of chambers. The diameter of the air cavity of cylindrical ionization chambers influences both the depth at which the maximum ionization is observed and the ionization per unit mass of air at this depth. The correction determined at depths of 50 mm and 100 mm is smaller than the correction currently used in many dosimetry protocols. The results presented here agree with the findings of Wang and Rogers

  14. Experimental investigation of the effect of air cavity size in cylindrical ionization chambers on the measurements in 60Co radiotherapy beams

    NASA Astrophysics Data System (ADS)

    Swanpalmer, John; Johansson, Karl-Axel

    2011-11-01

    In the late 1970s, Johansson et al (1978 Int. Symp. National and International Standardization of Radiation Dosimetry (Atlanta 1977) vol 2 (Vienna: IAEA) pp 243-70) reported experimentally determined displacement correction factors (pdis) for cylindrical ionization chamber dosimetry in 60Co and high-energy photon beams. These pdis factors have been implemented and are currently in use in a number of dosimetry protocols. However, the accuracy of these factors has recently been questioned by Wang and Rogers (2009a Phys. Med. Biol. 54 1609-20), who performed Monte Carlo simulations of the experiments performed by Johansson et al. They reported that the inaccuracy of the pdis factors originated from the normalization procedure used by Johansson et al. In their experiments, Johansson et al normalized the measured depth-ionization curves at the depth of maximum ionization for each of the different ionization chambers. In this study, we experimentally investigated the effect of air cavity size of cylindrical ionization chambers in a PMMA phantom and 60Co γ-beam. Two different pairs of air-filled cylindrical ionization chambers were used. The chambers in each pair had identical construction and materials but different air cavity volume (diameter). A 20 MeV electron beam was utilized to determine the ratio of the mass of air in the cavity of the two chambers in each pair. This ratio of the mass of air in each pair was then used to compare the ratios of the ionizations obtained at different depths in the PMMA phantom and 60Co γ-beam using the two pairs of chambers. The diameter of the air cavity of cylindrical ionization chambers influences both the depth at which the maximum ionization is observed and the ionization per unit mass of air at this depth. The correction determined at depths of 50 mm and 100 mm is smaller than the correction currently used in many dosimetry protocols. The results presented here agree with the findings of Wang and Rogers' Monte Carlo

  15. 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.

  16. Nanostructured indium tin oxide slides for small-molecule profiling and imaging mass spectrometry of metabolites by surface-assisted laser desorption ionization MS.

    PubMed

    López de Laorden, Carlos; Beloqui, Ana; Yate, Luis; Calvo, Javier; Puigivila, Maria; Llop, Jordi; Reichardt, Niels-Christian

    2015-01-01

    Due to their electrical conductivity and optical transparency, slides coated with a thin layer of indium tin oxide (ITO) are the standard substrate for protein imaging mass spectrometry on tissue samples by MALDI-TOF MS. We have now studied the rf magnetron sputtering deposition parameters to prepare ITO thin films on glass substrates with the required nanometric surface structure for their use in the matrix-free imaging of metabolites and small-molecule drugs, without affecting the transparency required for classical histology. The custom-made surfaces were characterized by atomic force microscopy, scanning electron microscopy, ellipsometry, UV, and laser desorption ionization MS (LDI-MS) and employed for the LDI-MS-based analysis of glycans and druglike molecules, the quantification of lactose in milk by isotopic dilution, and metabolite imaging on mouse brain tissue samples. PMID:25411795

  17. Potential Energy Curves and Collisions Integrals of Air Components. 2; Interactions Involving Ionized Atoms

    NASA Technical Reports Server (NTRS)

    Stallcop, James R.; Partridge, Harry; Levin, Eugene; Langhoff, Stephen R. (Technical Monitor)

    1995-01-01

    Collision integrals are fundamental quantities required to determine the transport properties of the environment surrounding aerospace vehicles in the upper atmosphere. These collision integrals can be determined as a function of temperature from the potential energy curves describing the atomic and molecular collisions. Ab initio calculations provide a practical method of computing the required interaction potentials. In this work we will discuss recent advances in scattering calculations with an emphasis on the accuracy that is obtainable. Results for interactions of the atoms and ionized atoms of nitrogen and oxygen will be reviewed and their application to the determination of transport properties, such as diffusion and viscosity coefficients, will be examined.

  18. Nonresonant ionization of oxygen molecules by femtosecond pulses: Plasma dynamics studied by time-resolved terahertz spectroscopy

    SciTech Connect

    Mics, Zoltan; Kadlec, Filip; Kuzel, Petr; Jungwirth, Pavel; Bradforth, Stephen E.; Apkarian, V. Ara

    2005-09-08

    We show that optical pump-terahertz probe spectroscopy is a direct experimental tool for exploring laser-induced ionization and plasma formation in gases. Plasma was produced in gaseous oxygen by focused amplified femtosecond pulses. The ionization mechanisms at 400- and 800-nm excitation wavelengths differ significantly being primarily of a multiphoton character in the former case and a strong-field process in the latter case. The generation of the plasma in the focal volume of the laser and its expansion on subnanosecond time scale is directly monitored through its density-dependent susceptibility. A Drude model used to evaluate the plasma densities and electron-scattering rates successfully captures the observations for a wide range of pump intensities. In addition, rotational fingerprints of molecular and ionic species were also observed in the spectra.

  19. Ionization Energies and Aqueous Redox Potentials of Organic Molecules: Comparison of DFT, Correlated ab Initio Theory and Pair Natural Orbital Approaches.

    PubMed

    Isegawa, Miho; Neese, Frank; Pantazis, Dimitrios A

    2016-05-10

    The calculation of redox potentials involves large energetic terms arising from gas phase ionization energies, thermodynamic contributions, and solvation energies of the reduced and oxidized species. In this work we study the performance of a wide range of wave function and density functional theory methods for the prediction of ionization energies and aqueous one-electron oxidation potentials of a set of 19 organic molecules. Emphasis is placed on evaluating methods that employ the computationally efficient local pair natural orbital (LPNO) approach, as well as several implementations of coupled cluster theory and explicitly correlated F12 methods. The electronic energies are combined with implicit solvation models for the solvation energies. With the exception of MP2 and its variants, which suffer from enormous errors arising at least partially from the poor Hartree-Fock reference, ionization energies can be systematically predicted with average errors below 0.1 eV for most of the correlated wave function based methods studies here, provided basis set extrapolation is performed. LPNO methods are the most efficient way to achieve this type of accuracy. DFT methods show in general larger errors and suffer from inconsistent behavior. The only exception is the M06-2X functional which is found to be competitive with the best LPNO-based approaches for ionization energies. Importantly, the limiting factor for the calculation of accurate redox potentials is the solvation energy. The errors in the predicted solvation energies by all continuum solvation models tested in this work dominate the final computed reduction potential, resulting in average errors typically in excess of 0.3 V and hence obscuring the gains that arise from choosing a more accurate electronic structure method.

  20. Coherent scattering of monochromatic RF radiation by ionization electrons of an extensive air shower

    SciTech Connect

    Filonenko, A. D.

    2013-10-15

    The possibility of detecting extensive air showers by recording and analyzing the radio pulse produced by the reradiation of a wave moving toward the cascade disk is considered. The coherent amplification of the scattered radiation in the direction of motion of the shower is shown to be due to a relativistic effect. An example of a real facility and its peculiarities are discussed.

  1. Non-proximate detection of small and large molecules by desorption electrospray ionization and desorption atmospheric pressure chemical ionization mass spectrometry: instrumentation and applications in forensics, chemistry, and biology.

    PubMed

    Cotte-Rodríguez, Ismael; Mulligan, Christopher C; Cooks, R Graham

    2007-09-15

    Ambient surfaces are examined by mass spectrometry at distances of up to 3 m from the instrument without any prior sample preparation. Non-proximate versions of the desorption electrospray ionization (DESI) and desorption atmospheric pressure chemical ionization experiments are shown to allow rapid, sensitive, and selective detection of trace amounts of active ingredients in pharmaceutical drug formulations, illicit drugs (methamphetamine, cocaine, and diacetylmorphine), organic salts, peptides, chemical warfare agent simulants, and other small organic compounds. Utilizing an ion transport tube to transport analyte ions to the mass spectrometer, nonproximate DESI allows one to collect high-quality, largely interference-free spectra with signal-to-noise (S/N) ratios of more than 100. High selectivity is achieved by tandem mass spectrometry and by reactive DESI, a variant experiment in which reagents added into the solvent spray allow bond-forming reactions with the analyte. Ion/molecule reactions were found to selectively suppress the response of mixture components other than the analyte of interest in nonproximate-DESI. Flexible ion transport tubing is also investigated, allowing performance similar to stainless steel tubing in the transport of ions from the sample to the mass spectrometer. Transfer tube temperature effects are examined. A multiple sprayer DESI source capable of analyzing a larger sample area was evaluated to decrease the sampling time and increase sample throughput. Low nanogram detection limits were obtained for the compounds studied from a wide variety of surfaces, even those present in complex matrixes.

  2. Standoff alpha radiation detection via excited state absorption of air

    SciTech Connect

    Yao, Jimmy; Yin, Stuart Shizhuo; Brenizer, Jack; Hui, Rongqing

    2013-06-24

    A standoff alpha radiation detection technique based on the physical mechanism of excited state absorption of air molecules was explored and is presented in this paper. Instead of directly detecting the radiation via measuring the intensity of radiation induced air fluorescence, the radiation is detected via the excited state absorption of alpha radiation excited/ionized air molecules. Both theoretical analyses and experimental verifications were conducted. The experimental results confirmed that the radiation could be detected via excited state absorption of radiation excited/ionized air molecules at a 10 m standoff distance, which was consistent with the theoretical analyses.

  3. Will Allis Prize for the Study of Ionized Gases Lecture: Electron and Photon Collisions with Atoms and Molecules

    NASA Astrophysics Data System (ADS)

    Burke, Philip G.

    2012-06-01

    After a brief historical introduction this talk will review the broad range of collision processes involving electron and photon collisions with atoms and molecules that are now being considered. Their application in the analysis of astronomical spectra, atmospheric observations and laboratory plasmas will be considered. The talk will review the R-matrix computational method which has been widely used by international collaborations and by other scientists in the field to obtain accurate scattering amplitudes and cross sections of importance in these applications. Results of some recent calculations of electron and photon collisions with atoms and molecules will be presented. In conclusion some challenges for future research will be briefly discussed.

  4. AUTOMATED DECONVOLUTION OF COMPOSITE MASS SPECTRA OBTAINED WITH AN OPEN-AIR IONIZATIONS SOURCE BASED ON EXACT MASSES AND RELATIVE ISOTIPIC ABUNDANCES

    EPA Science Inventory

    Chemicals dispersed by accidental, deliberate, or weather-related events must be rapidly identified to assess health risks. Mass spectra from high levels of analytes obtained using rapid, open-air ionization by a Direct Analysis in Real Time (DART®) ion source often contain

  5. REAL TIME, ON-LINE CHARACTERIZATION OF DIESEL GENERATOR AIR TOXIC EMISSIONS BY RESONANCE ENHANCED MULTI-PHOTON IONIZATION TIME OF FLIGHT MASS SPECTROMETRY

    EPA Science Inventory

    The laser based resonance, enhanced multi-photon ionization time-of-flight mass spectrometry (REMPI-TOFMS) technique has been applied to the exhaust gas stream of a diesel generator to measure, in real time, concentration levels of aromatic air toxics. Volatile organic compounds ...

  6. Reference dosimetry at the Australian Synchrotron's imaging and medical beamline using free-air ionization chamber measurements and theoretical predictions of air kerma rate and half value layer

    SciTech Connect

    Crosbie, Jeffrey C.; Rogers, Peter A. W.; Stevenson, Andrew W.; Hall, Christopher J.; Lye, Jessica E.; Nordstroem, Terese; Midgley, Stewart M.; Lewis, Robert A.

    2013-06-15

    Purpose: Novel, preclinical radiotherapy modalities are being developed at synchrotrons around the world, most notably stereotactic synchrotron radiation therapy and microbeam radiotherapy at the European Synchrotron Radiation Facility in Grenoble, France. The imaging and medical beamline (IMBL) at the Australian Synchrotron has recently become available for preclinical radiotherapy and imaging research with clinical trials, a distinct possibility in the coming years. The aim of this present study was to accurately characterize the synchrotron-generated x-ray beam for the purposes of air kerma-based absolute dosimetry. Methods: The authors used a theoretical model of the energy spectrum from the wiggler source and validated this model by comparing the transmission through copper absorbers (0.1-3.0 mm) against real measurements conducted at the beamline. The authors used a low energy free air ionization chamber (LEFAC) from the Australian Radiation Protection and Nuclear Safety Agency and a commercially available free air chamber (ADC-105) for the measurements. The dimensions of these two chambers are different from one another requiring careful consideration of correction factors. Results: Measured and calculated half value layer (HVL) and air kerma rates differed by less than 3% for the LEFAC when the ion chamber readings were corrected for electron energy loss and ion recombination. The agreement between measured and predicted air kerma rates was less satisfactory for the ADC-105 chamber, however. The LEFAC and ADC measurements produced a first half value layer of 0.405 {+-} 0.015 and 0.412 {+-} 0.016 mm Cu, respectively, compared to the theoretical prediction of 0.427 {+-} 0.012 mm Cu. The theoretical model based upon a spectrum calculator derived a mean beam energy of 61.4 keV with a first half value layer of approximately 30 mm in water. Conclusions: The authors showed in this study their ability to verify the predicted air kerma rate and x-ray attenuation

  7. High resolution UV resonance enhanced two-photon ionization spectroscopy with mass selection of biologically relevant molecules in the gas phase

    NASA Astrophysics Data System (ADS)

    Chervenkov, S.; Wang, P. Q.; Karaminkov, R.; Chakraborty, T.; Braun, Juergen E.; Neusser, Hans J.

    2005-04-01

    The high resolution Doppler-free resonance-enhanced two-photon ionization (R2PI) spectroscopy with mass selection of jet-cooled (2-12 K) molecular species is a powerful experimental method providing comprehensive information on both isolated molecules and molecular clusters. We have demonstrated for the first time that this technique can be applied to large molecules and provides detailed information on their conformational structure. It allows rotationally resolved (FWHM = 70 MHz) spectra of the vibronic bands of the S1<--S0 electronic transition of the studied molecular systems to be measured. A specially designed computer-assisted fitting routine based on genetic algorithms is used to determine their rotational constants in the ground and excited electronic states, respectively, and the transition moment ratio. To interpret the experimental information and to discriminate and unambiguously assign the observed approach to the study of the neurotransmitter molecule, ephedrine. The results elucidate the role of the intramolecular hydrogen bonds stabilizing the respective conformations and affecting their intrinsic properties.

  8. Atmospheric Ionizing Radiation (AIR): Analysis, Results, and Lessons Learned From the June 1997 ER-2 Campaign

    NASA Technical Reports Server (NTRS)

    Wilson, J. W. (Editor); Jones, I. W. (Editor); Maiden, D. L. (Editor); Goldhagen, P. (Editor)

    2003-01-01

    The United States initiated a program to assess the technology required for an environmentally safe and operationally efficient High Speed Civil Transport (HSCT) for entrance on the world market after the turn of the century. Due to the changing regulations on radiation exposures and the growing concerns over uncertainty in our knowledge of atmospheric radiations, the NASA High Speed Research Project Office (HSRPO) commissioned a review of "Radiation Exposure and High-Altitude Flight" by the National Council on Radiation Protection and Measurements (NCRP). On the basis of the NCRP recommendations, the HSRPO funded a flight experiment to resolve the environmental uncertainty in the atmospheric ionizing radiation levels as a step in developing an approach to minimize the radiation impact on HSCT operations. To minimize costs in this project, an international investigator approach was taken to assure coverage with instrument sensitivity across the range of particle types and energies to allow unique characterization of the diverse radiation components. The present workshop is a result of the flight measurements made at the maximum intensity of the solar cycle modulated background radiation levels during the month of June 1997.

  9. Single- and two-centre effects in fully differential cross sections for single ionization of H2 molecules by 75 keV protons

    NASA Astrophysics Data System (ADS)

    Ciappina, M. F.; Tachino, C. A.; Rivarola, R. D.; Sharma, S.; Schulz, M.

    2015-06-01

    We present theoretical calculations of single ionization of H2 molecules by 75 keV proton impact. The computed fully differential cross sections for different electron ejection geometries and projectile kinematical conditions are compared with recent measurements made by Hasan et al (2014 J. Phys. B: At. Mol. Opt. Phys. 47 215201). We employ a molecular version of the continuum distorted wave-eikonal initial state model, where all the interactions present in the exit channel are considered on an equal footing. In addition, our approach allows us to incorporate different interference terms and to assess their influence. Overall, the agreement between experiment and theory is better than for the case of more sophisticated schemes for coplanar geometries.

  10. Fundamental studies of matrix-assisted laser desorption/ionization, using time-of-flight mass spectrometry to identify biological molecules

    SciTech Connect

    Eades, D.; Wruck, D.; Gregg, H.

    1996-11-11

    MALDI MS was developed as a way of getting molecular weight information on small quantities (picomole to femtomole levels) of high-mass, thermally labile macromolecules. While most other analytical MS ionization techniques cause fragmentation, decomposition, or multiple charging, MALDI efficiently places intact macromolecules into the gas phase with little fragmentation or rearrangement. This project had 3 objectives: establish the MALDI capability at LLNL, perform fundamental studies of analyte-matrix interactions, and apply the technique for biochemical research. A retired time-of-flight instrument was adapted for MALDI analyses, relevant parameters influencing the MALDI process were identified for further study (matrix molar absorptivity, sample crystal preparation), and collaborations were established with research groups in the Biology and Biotechnology Research Program at LLNL. In MALDI, the macromolecule of interest is mixed with a high-molar excess (1:100 to 1:10,000) of an organic matrix which readily absorbs energy at the wavelength corresponding to a UV laser. Upon laser irradiation, the matrix absorbs the majority of the energy, causing it to desorb from the surface and gently release the macromolecule into the gas phase with little or no fragmentation. Once in the gas phase, ion-molecule reactions between excited matrix and neutral macromolecules generated ionized analyte species which then can be focused into a MS for detection.

  11. A possibility of a protein-bound water molecule as the ionizable group responsible for pKe at the alkaline side in human matrix metalloproteinase 7 activity.

    PubMed

    Morishima, Aiko; Yasukawa, Kiyoshi; Inouye, Kuniyo

    2012-05-01

    Human matrix metalloproteinase 7 (MMP-7) activity exhibits broad bell-shaped pH profile with the acidic and alkaline pK(a) (pK(e1) and pK(e2)) values of about 4 and 10. The ionizable group for pK(e2) was assigned to Lys or Arg by thermodynamic analysis; however, no such residues are present in the active site. Hence, based on the crystal structure, we hypothesized that a water molecule bound to the main-chain nitrogen of Ala162 (W1) or the main-chain carbonyl oxygen of Pro217 (W2) is a candidate for the ionizable group for pK(e2) [Takeharu, H. et al. (2011) Biochim. Biophys. Acta 1814, 1940-1946]. In this study, we inspected this hypothesis. In the hydrolysis of (7-methoxycoumarin-4-yl)acetyl-L-Pro-L-Leu-Gly-L-Leu-[N(3)-(2,4-dinitrophenyl)-L-2,3-diaminopropionyl]-L-Ala-L-Arg-NH(2), all 19 variants, in which one of all Lys and Arg residues was replaced by Ala, retained activity, indicating that neither Lys nor Arg is the ionizable group. pK(e2) values of A162S, A162V and A162G were 9.6 ± 0.1, 9.5 ± 0.1 and 10.4 ± 0.2, respectively, different from that of wild-type MMP-7 (WT) (9.9 ± 0.1) by 0.3-0.5 pH unit, and those of P217S, P217V and P217G were 10.1 ± 0.1, 9.8 ± 0.1 and 9.7 ± 0.1, respectively, different from that of WT by 0.1-0.2 pH unit. These results suggest a possibility of W1 or W2 as the ionizable group for pK(e2).

  12. Intramolecular interactions of L-phenylalanine: Valence ionization spectra and orbital momentum distributions of its fragment molecules.

    PubMed

    Ganesan, Aravindhan; Wang, Feng; Falzon, Chantal

    2011-02-01

    Intramolecular interactions between fragments of L-phenylalanine, i.e., phenyl and alaninyl, have been investigated using dual space analysis (DSA) quantum mechanically. Valence space photoelectron spectra (PES), orbital energy topology and correlation diagram, as well as orbital momentum distributions (MDs) of L-phenylalanine, benzene and L-alanine are studied using density functional theory methods. While fully resolved experimental PES of L-phenylalanine is not yet available, our simulated PES reproduces major features of the experimental measurement. For benzene, the simulated orbital MDs for 1e(1g) and 1a(2u) orbitals also agree well with those measured using electron momentum spectra. Our theoretical models are then applied to reveal intramolecular interactions of the species on an orbital base, using DSA. Valence orbitals of L-phenylalanine can be essentially deduced into contributions from its fragments such as phenyl and alaninyl as well as their interactions. The fragment orbitals inherit properties of their parent species in energy and shape (ie., MDs). Phenylalanine orbitals show strong bonding in the energy range of 14-20 eV, rather than outside of this region. This study presents a competent orbital based fragments-in-molecules picture in the valence space, which supports the fragment molecular orbital picture and building block principle in valence space. The optimized structures of the molecules are represented using the recently developed interactive 3D-PDF technique.

  13. Formation of ultracold {sup 7}Li{sup 85}Rb molecules in the lowest triplet electronic state by photoassociation and their detection by ionization spectroscopy

    SciTech Connect

    Altaf, Adeel Dutta, Sourav; Lorenz, John; Pérez-Ríos, Jesús; Chen, Yong P.; Elliott, D. S.

    2015-03-21

    We report the formation of ultracold {sup 7}Li{sup 85}Rb molecules in the a{sup 3}Σ{sup +} electronic state by photoassociation (PA) and their detection via resonantly enhanced multiphoton ionization (REMPI). With our dual-species Li and Rb magneto-optical trap apparatus, we detect PA resonances with binding energies up to ∼62 cm{sup −1} below the {sup 7}Li 2s {sup 2}S{sub 1/2} + {sup 85}Rb 5p {sup 2}P{sub 1/2} asymptote. In addition, we use REMPI spectroscopy to probe the a{sup 3}Σ{sup +} state and excited electronic 3{sup 3}Π and 4{sup 3}Σ{sup +} states and identify a{sup 3}Σ{sup +} (v″ = 7–13), 3{sup 3}Π (v{sub Π}′ = 0–10), and 4{sup 3}Σ{sup +} (v{sub Σ}′ = 0–5) vibrational levels. Our line assignments agree well with ab initio calculations. These preliminary spectroscopic studies on previously unobserved electronic states are crucial to discovering transition pathways for transferring ultracold LiRb molecules created via PA to deeply bound rovibrational levels of the electronic ground state.

  14. Design, Modeling, Fabrication, and Evaluation of the Air Amplifier for Improved Detection of Biomolecules by Electrospray Ionization Mass Spectrometry

    PubMed Central

    Robichaud, Guillaume; Dixon, R. Brent; Potturi, Amarnatha S.; Cassidy, Dan; Edwards, Jack R.; Sohn, Alex; Dow, Thomas A.; Muddiman, David C.

    2010-01-01

    Through a multi-disciplinary approach, the air amplifier is being evolved as a highly engineered device to improve detection limits of biomolecules when using electrospray ionization. Several key aspects have driven the modifications to the device through experimentation and simulations. We have developed a computer simulation that accurately portrays actual conditions and the results from these simulations are corroborated by the experimental data. These computer simulations can be used to predict outcomes from future designs resulting in a design process that is efficient in terms of financial cost and time. We have fabricated a new device with annular gap control over a range of 50 to 70 μm using piezoelectric actuators. This has enabled us to obtain better aerodynamic performance when compared to the previous design (2× more vacuum) and also more reproducible results. This is allowing us to study a broader experimental space than the previous design which is critical in guiding future directions. This work also presents and explains the principles behind a fractional factorial design of experiments methodology for testing a large number of experimental parameters in an orderly and efficient manner to understand and optimize the critical parameters that lead to obtain improved detection limits while minimizing the number of experiments performed. Preliminary results showed that several folds of improvements could be obtained for certain condition of operations (up to 34 folds). PMID:21499524

  15. Dynamics of ionization processes in high-pressure nitrogen, air, and SF6 during a subnanosecond breakdown initiated by runaway electrons

    NASA Astrophysics Data System (ADS)

    Tarasenko, V. F.; Beloplotov, D. V.; Lomaev, M. I.

    2015-10-01

    The dynamics of ionization processes in high-pressure nitrogen, air, and SF6 during breakdown of a gap with a nonuniform distribution of the electric field by nanosecond high-voltage pulses was studied experimentally. Measurements of the amplitude and temporal characteristics of a diffuse discharge and its radiation with a subnanosecond time resolution have shown that, at any polarity of the electrode with a small curvature radius, breakdown of the gap occurs via two ionization waves, the first of which is initiated by runaway electrons. For a voltage pulse with an ˜500-ps front, UV radiation from different zones of a diffuse discharge is measured with a subnanosecond time resolution. It is shown that the propagation velocity of the first ionization wave increases after its front has passed one-half of the gap, as well as when the pressure in the discharge chamber is reduced and/or when SF6 is replaced with air or nitrogen. It is found that, at nitrogen pressures of 0.4 and 0.7 MPa and the positive polarity of the high-voltage electrode with a small curvature radius, the ionization wave forms with a larger (˜30 ps) time delay with respect to applying the voltage pulse to the gap than at the negative polarity. The velocity of the second ionization wave propagating from the plane electrode is measured. In a discharge in nitrogen at a pressure of 0.7 MPa, this velocity is found to be ˜10 cm/ns. It is shown that, as the nitrogen pressure increases to 0.7 MPa, the propagation velocity of the front of the first ionization wave at the positive polarity of the electrode with a small curvature radius becomes lower than that at the negative polarity.

  16. Dynamics of ionization processes in high-pressure nitrogen, air, and SF{sub 6} during a subnanosecond breakdown initiated by runaway electrons

    SciTech Connect

    Tarasenko, V. F. Beloplotov, D. V.; Lomaev, M. I.

    2015-10-15

    The dynamics of ionization processes in high-pressure nitrogen, air, and SF{sub 6} during breakdown of a gap with a nonuniform distribution of the electric field by nanosecond high-voltage pulses was studied experimentally. Measurements of the amplitude and temporal characteristics of a diffuse discharge and its radiation with a subnanosecond time resolution have shown that, at any polarity of the electrode with a small curvature radius, breakdown of the gap occurs via two ionization waves, the first of which is initiated by runaway electrons. For a voltage pulse with an ∼500-ps front, UV radiation from different zones of a diffuse discharge is measured with a subnanosecond time resolution. It is shown that the propagation velocity of the first ionization wave increases after its front has passed one-half of the gap, as well as when the pressure in the discharge chamber is reduced and/or when SF{sub 6} is replaced with air or nitrogen. It is found that, at nitrogen pressures of 0.4 and 0.7 MPa and the positive polarity of the high-voltage electrode with a small curvature radius, the ionization wave forms with a larger (∼30 ps) time delay with respect to applying the voltage pulse to the gap than at the negative polarity. The velocity of the second ionization wave propagating from the plane electrode is measured. In a discharge in nitrogen at a pressure of 0.7 MPa, this velocity is found to be ∼10 cm/ns. It is shown that, as the nitrogen pressure increases to 0.7 MPa, the propagation velocity of the front of the first ionization wave at the positive polarity of the electrode with a small curvature radius becomes lower than that at the negative polarity.

  17. Easy dual-mode ambient mass spectrometry with Venturi self-pumping, canned air, disposable parts and voltage-free sonic-spray ionization.

    PubMed

    Schwab, Nicolas V; Porcari, Andreia M; Coelho, Mirela B; Schmidt, Eduardo M; Jara, Jose L; Visentainer, Jesui V; Eberlin, Marcos N

    2012-06-01

    An exceptionally easy to assemble source for ambient mass spectrometry is described. Based on Venturi easy ambient sonic-spray ionization (V-EASI), the source was further simplified by the use of a can of compressed air which simultaneously provides solution or solvent Venturi self-pumping and continuous, stable and abundant low-noise ion signal via voltage-free sonic-spraying. Further simplification was also attained by the use of inexpensive and readily commercially available parts: a surgical 2-way catheter, an aerosol can of compressed air, a 30 cm long fused-silica capillary and a hypodermic needle. This "Spartan" V-EASI source seems to offer one of the easiest and cheapest ways to make ions for ambient desorption/ionization mass spectrometry analysis of both liquid and solid samples. PMID:22349120

  18. Design of an integrated sensor system for the detection of traces of different molecules in the air

    NASA Astrophysics Data System (ADS)

    Strle, D.; Muševič, I.

    2015-04-01

    This article presents the design of a miniature detection system and its associated signal processing electronics, which can detect and selectively recognize vapor traces of different materials in the air - including explosives. It is based on the array of surface-functionalized COMB capacitive sensors and extremely low noise, analog, integrated electronic circuit, hardwired digital signal processing hardware and additional software running on a PC. The instrument is sensitive and selective, consumes a minimum amount of energy, is very small (few mm3) and cheap to produce in large quantities, and is insensitive to mechanical influences. Using an electronic detection system built of low noise analog front-end and hard-wired digital signal processing, it is possible to detect less than 0.3ppt of TNT molecules in the atmosphere (3 TNT molecules in 1013 molecules of the air) at 25°C on a 1 Hz bandwidth using very small volume and approx. 10 mA current from a 5V supply voltage. The sensors are implemented in a modified MEMS process and analog electronics in 0.18 um CMOS technology.

  19. Formic and Acetic Acid Observations over Colorado by Chemical Ionization Mass Spectrometry and Organic Acids' Role in Air Quality

    NASA Astrophysics Data System (ADS)

    Treadaway, V.; O'Sullivan, D. W.; Heikes, B.; Silwal, I.; McNeill, A.

    2015-12-01

    Formic acid (HFo) and acetic acid (HAc) have both natural and anthropogenic sources and a role in the atmospheric processing of carbon. These organic acids also have an increasing importance in setting the acidity of rain and snow as precipitation nitrate and sulfate concentrations have decreased. Primary emissions for both organic acids include biomass burning, agriculture, and motor vehicle emissions. Secondary production is also a substantial source for both acids especially from biogenic precursors, secondary organic aerosols (SOAs), and photochemical production from volatile organic compounds (VOCs) and oxygenated volatile organic compounds (OVOCs). Chemical transport models underestimate organic acid concentrations and recent research has sought to develop additional production mechanisms. Here we report HFo and HAc measurements during two campaigns over Colorado using the peroxide chemical ionization mass spectrometer (PCIMS). Iodide clusters of both HFo and HAc were recorded at mass-to-charge ratios of 173 and 187, respectively. The PCIMS was flown aboard the NCAR Gulfstream-V platform during the Deep Convective Clouds and Chemistry Experiment (DC3) and aboard the NCAR C-130 during the Front Range Air Pollution and Photochemistry Experiment (FRAPPE). The DC3 observations were made in May and June 2012 extending from the surface to 13 km over the central and eastern United States. FRAPPE observations were made in July and August 2014 from the surface to 7 km over Colorado. DC3 measurements reported here are focused over the Colorado Front Range and complement the FRAPPE observations. DC3 HFo altitude profiles are characterized by a decrease up to 6 km followed by an increase either back to boundary layer mixing ratio values or higher (a "C" shape). Organic acid measurements from both campaigns are interpreted with an emphasis on emission sources (both natural and anthropogenic) over Colorado and in situ photochemical production especially ozone precursors.

  20. NR2 and P3+: Accurate, Efficient Electron-Propagator Methods for Calculating Valence, Vertical Ionization Energies of Closed-Shell Molecules.

    PubMed

    Corzo, H H; Galano, Annia; Dolgounitcheva, O; Zakrzewski, V G; Ortiz, J V

    2015-08-20

    Two accurate and computationally efficient electron-propagator (EP) methods for calculating the valence, vertical ionization energies (VIEs) of closed-shell molecules have been identified through comparisons with related approximations. VIEs of a representative set of closed-shell molecules were calculated with EP methods using 10 basis sets. The most easily executed method, the diagonal, second-order (D2) EP approximation, produces results that steadily rise as basis sets are improved toward values based on extrapolated coupled-cluster singles and doubles plus perturbative triples calculations, but its mean errors remain unacceptably large. The outer valence Green function, partial third-order and renormalized partial third-order methods (P3+), which employ the diagonal self-energy approximation, produce markedly better results but have a greater tendency to overestimate VIEs with larger basis sets. The best combination of accuracy and efficiency with a diagonal self-energy matrix is the P3+ approximation, which exhibits the best trends with respect to basis-set saturation. Several renormalized methods with more flexible nondiagonal self-energies also have been examined: the two-particle, one-hole Tamm-Dancoff approximation (2ph-TDA), the third-order algebraic diagrammatic construction or ADC(3), the renormalized third-order (3+) method, and the nondiagonal second-order renormalized (NR2) approximation. Like D2, 2ph-TDA produces steady improvements with basis set augmentation, but its average errors are too large. Errors obtained with 3+ and ADC(3) are smaller on average than those of 2ph-TDA. These methods also have a greater tendency to overestimate VIEs with larger basis sets. The smallest average errors occur for the NR2 approximation; these errors decrease steadily with basis augmentations. As basis sets approach saturation, NR2 becomes the most accurate and efficient method with a nondiagonal self-energy. PMID:26226061

  1. NR2 and P3+: Accurate, Efficient Electron-Propagator Methods for Calculating Valence, Vertical Ionization Energies of Closed-Shell Molecules.

    PubMed

    Corzo, H H; Galano, Annia; Dolgounitcheva, O; Zakrzewski, V G; Ortiz, J V

    2015-08-20

    Two accurate and computationally efficient electron-propagator (EP) methods for calculating the valence, vertical ionization energies (VIEs) of closed-shell molecules have been identified through comparisons with related approximations. VIEs of a representative set of closed-shell molecules were calculated with EP methods using 10 basis sets. The most easily executed method, the diagonal, second-order (D2) EP approximation, produces results that steadily rise as basis sets are improved toward values based on extrapolated coupled-cluster singles and doubles plus perturbative triples calculations, but its mean errors remain unacceptably large. The outer valence Green function, partial third-order and renormalized partial third-order methods (P3+), which employ the diagonal self-energy approximation, produce markedly better results but have a greater tendency to overestimate VIEs with larger basis sets. The best combination of accuracy and efficiency with a diagonal self-energy matrix is the P3+ approximation, which exhibits the best trends with respect to basis-set saturation. Several renormalized methods with more flexible nondiagonal self-energies also have been examined: the two-particle, one-hole Tamm-Dancoff approximation (2ph-TDA), the third-order algebraic diagrammatic construction or ADC(3), the renormalized third-order (3+) method, and the nondiagonal second-order renormalized (NR2) approximation. Like D2, 2ph-TDA produces steady improvements with basis set augmentation, but its average errors are too large. Errors obtained with 3+ and ADC(3) are smaller on average than those of 2ph-TDA. These methods also have a greater tendency to overestimate VIEs with larger basis sets. The smallest average errors occur for the NR2 approximation; these errors decrease steadily with basis augmentations. As basis sets approach saturation, NR2 becomes the most accurate and efficient method with a nondiagonal self-energy.

  2. Photoinduced nucleation: a novel tool for detecting molecules in air at ultra-low concentrations

    DOEpatents

    Katz, Joseph L.; Lihavainen, Heikki; Rudek, Markus M.; Salter, Brian C.

    2002-01-01

    A method and apparatus for determining the presence of molecules in a gas at concentrations of less than about 100 ppb. Light having wavelengths in the range from about 200 nm to about 350 nm is used to illuminate a flowing sample of the gas causing the molecules if present to form clusters. A mixture of the illuminated gas and a vapor is cooled until the vapor is supersaturated so that there is a small rate of homogeneous nucleation. The supersaturated vapor condenses on the clusters thus causing the clusters to grow to a size sufficient to be counted by light scattering and then the clusters are counted.

  3. Two-photon double-ionization of the H2 molecule in light perpindicular to the internuclear axis: effects of pulse duration

    NASA Astrophysics Data System (ADS)

    Guan, Xiaoxu; Bartschat, Klaus; Schneider, Barry; Koesterke, Lars

    2014-05-01

    Earlier, we solved the time-dependent Schrödinger equation to calculate the two-photon double ionization of the hydrogen molecule induced by non-sequential absorption of photons with a central energy of 30 eV in a short laser pulse lasting for about 1.6 femtoseconds. The linear polarization of the radiation was aligned with the internuclear axis. At the equilibrium distance Req, several doubly excited 1Σg , u states, accessible through photon absorption,lie about 30 eV above the X1Σg ground state. These states are likely responsible for the significant disagreement seen in the literature for previous results on both angle-integrated and angle-differential cross sections. Here we continue to explore the fundamental role of doubly excited states on the two-photon break-up process,now for the even more difficult problem of laser polarization perpendicular to the internuclear axis. Such studies require relatively long laser pulses, thus making the calculations computationally very challenging.

  4. Immunohistochemical expression of ionized calcium binding adapter molecule 1 in cutaneous histiocytic proliferative, neoplastic and inflammatory disorders of dogs and cats.

    PubMed

    Pierezan, F; Mansell, J; Ambrus, A; Rodrigues Hoffmann, A

    2014-11-01

    Ionized calcium-binding adapter molecule 1 (Iba1) has been used widely as a marker for microglial cells and, recently, was also recognized as a 'pan-macrophage marker', as it is expressed by all subpopulations of cells of the monocyte/macrophage lineage. To determine the specificity of Iba1 as an immunohistochemical marker for canine and feline histiocytic proliferative, neoplastic and inflammatory disorders of the skin, we evaluated its expression in two types of histiocytic tumours, two non-neoplastic histiocytic proliferative conditions, one case of granulomatous dermatitis and four non-histiocytic tumours. Cells of the monocyte/macrophage lineage in all cases of canine cutaneous histiocytoma (9/9), reactive histiocytosis (9/9), histiocytic sarcomas (5/5), feline progressive dendritic cell histiocytosis (3/3) and macrophages in cutaneous mycobacteriosis (7/7) showed strong cytoplasmic expression of Iba1. Neoplastic cells of melanomas (10/10), lymphomas (7/7), mast cell tumours (7/7) and plasmacytomas (4/4) did not express Iba1. Iba1 is therefore a useful marker of cells of the monocyte/macrophage lineage in canine and feline inflammatory, proliferative and neoplastic conditions and can be used to identify these cells in formalin-fixed, paraffin wax-embedded tissues. Iba1 is not able to differentiate between macrophages and dendritic antigen presenting cells and expression does not allow classification of these histiocytic disorders. PMID:25172051

  5. O 1s excitation and ionization processes in the CO2 molecule studied via detection of low-energy fluorescence emission

    NASA Astrophysics Data System (ADS)

    Kivimäki, A.; Alvarez-Ruiz, J.; Wasowicz, T. J.; Callegari, C.; de Simone, M.; Alagia, M.; Richter, R.; Coreno, M.

    2011-08-01

    Oxygen 1s excitation and ionization processes in the CO2 molecule have been studied with dispersed and non-dispersed fluorescence spectroscopy as well as with the vacuum ultraviolet (VUV) photon-photoion coincidence technique. The intensity of the neutral O emission line at 845 nm shows particular sensitivity to core-to-Rydberg excitations and core-valence double excitations, while shape resonances are suppressed. In contrast, the partial fluorescence yield in the wavelength window 300-650 nm and the excitation functions of selected O+ and C+ emission lines in the wavelength range 400-500 nm display all of the absorption features. The relative intensity of ionic emission in the visible range increases towards higher photon energies, which is attributed to O 1s shake-off photoionization. VUV photon-photoion coincidence spectra reveal major contributions from the C+ and O+ ions and a minor contribution from C2 +. No conclusive changes in the intensity ratios among the different ions are observed above the O 1s threshold. The line shape of the VUV-O+ coincidence peak in the mass spectrum carries some information on the initial core excitation.

  6. Higher-Sensitivity Ionization Trace-Species Detector

    NASA Technical Reports Server (NTRS)

    Boumsellek, Said; Chutjian, Ara

    1995-01-01

    Electron source and electron optics of reversal electron-attachment detector modified to increase sensitivity. Original version described in "High-Sensitivity Ionization Trace-Species Detector" (NPO-17596). Used to detect molecules of particular chemical species of interest (e.g., narcotics, explosives, or organic wastes) present in air at low concentrations, and known to attach extremely low-energy electrons. Apparatus does this by ionizing molecules from sampled atmosphere, then detecting ions of species of interest. Detector features indirectly heated spherical cathode and redesigned electron optics, together, deliver more electrons at low kinetic energy to reversal plane, R. Greater electron current generates more ions for detection.

  7. Fuel cell with ionization membrane

    NASA Technical Reports Server (NTRS)

    Hartley, Frank T. (Inventor)

    2007-01-01

    A fuel cell is disclosed comprising an ionization membrane having at least one area through which gas is passed, and which ionizes the gas passing therethrough, and a cathode for receiving the ions generated by the ionization membrane. The ionization membrane may include one or more openings in the membrane with electrodes that are located closer than a mean free path of molecules within the gas to be ionized. Methods of manufacture are also provided.

  8. Probing Shear Thinning Behaviors of IgG Molecules at the Air-Water Interface via Rheological Methods.

    PubMed

    Gleason, Camille; Yee, Chanel; Masatani, Peter; Middaugh, C Russell; Vance, Aylin

    2016-01-19

    Shear thinning behavior, often observed in shear viscosity tests of IgG therapeutic molecules, could lead to significant disparities in the projections for the viscosity profile of a molecule. Despite its importance, molecular determinants of sheer thinning in protein suspensions are largely unknown. To better understand the factors influencing sheer thinning, viscosity profiles of IgG1 and IgG2 molecules were monitored over a wide range of bulk concentrations (0.007-70 mg/mL). The degree of shear-thinning of 70 and 0.007 mg/mL samples was minimal in comparison to the 0.7 mg/mL solution for both IgG molecules. These observations suggest that bulk concentration alone does not determine the degree of sheer thinning, and additional factors play a role. Additional data reveals, within a threshold range of concentrations, that a strong correlation exists between the degree of shear thinning and the surface area to volume (SA:V) ratio of an IgG sample exposed to the interface. The influence of the interface, however, diminishes when the bulk concentration falls outside this concentration window. Also revealed by interfacial oscillatory rheological testing, both IgG molecules showed solid-like behavior (G'i) at the air-water interface at 0.7 mg/mL, whereas liquid-like behavior (G″i) was dominant at 0.007 and 70 mg/mL concentrations. These observations imply that the lack of solid-like behavior was due to the absence of a network structure. Likewise the addition of polysorbate 20 (PS20) to the 0.7 mg/mL solutions decreased the degree of shear thinning by disrupting the network structure at the interface. Taken together, the results presented here suggest that, although shear thinning behavior is a manifestation of an interfacial, rather than a bulk, phenomenon, the extent of it depends on how susceptible the surface molecules are to the air-water interface, where the surface molecular structures are influenced by the bulk properties.

  9. Cyclic organic peroxides identification and trace analysis by Raman microscopy and open-air chemical ionization mass spectrometry

    NASA Astrophysics Data System (ADS)

    Pena-Quevedo, Alvaro Javier

    The persistent use of cyclic organic peroxides in explosive devices has increased the interest in study these compounds. Development of methodologies for the detection of triacetone triperoxide (TATP) and hexamethylene triperoxide diamine (HMTD) has become an urgent priority. However, differences in physical properties between cyclic organic peroxides make difficult the development of a general method for peroxide analysis and detection. Following this urgency, the first general technique for the analysis of any peroxide, regarding its structural differences is reported. Characterization and detection of TATP and HMTD was performed using an Open-Air Chemical Ionization High-Resolution Time-of-Flight Mass Spectrometer. The first spectrometric analysis for tetramethylene diperoxide dicarbamide (TMDD) and other nitrogen based peroxides using Raman Microscopy and Mass Spectrometry is reported. Analysis of cyclic peroxides by GC-MS was also conducted to compare results with OACI-HRTOF data. In the OACI mass spectrum, HMTD showed a clear signal at m/z 209 MH + and a small adduct peak at m/z 226 [M+NH4]+ that allowed its detection in commercial standard solutions and lab made standards. TMDD presented a molecular peak of m/z 237 MH+ and an adduct peak of m/z 254 [M+NH4]+. TATP showed a single peak at m/z 240 [M+NH4]+, while the peak of m/z 223 or 222 was completely absent. This evidence suggests that triperoxides are stabilized by the ammonium ion. TATP samples with deuterium enrichment were analyzed to compare results that could differentiate from HMTD. Raman microscopy was used as a complementary characterization method and was an essential tool for cyclic peroxides identification, particularly for those which could not be extensively purified. All samples were characterized by Raman spectroscopy to confirm the Mass Spectrometry results. Peroxide O-O vibrations were observed around 750-970 cm-1. D18-TATP studies had identified ketone triperoxide nu(O-O) vibration around

  10. Submicrometer particle removal indoors by a novel electrostatic precipitator with high clean air delivery rate, low ozone emissions, and carbon fiber ionizer.

    PubMed

    Kim, H-J; Han, B; Kim, Y-J; Oda, T; Won, H

    2013-10-01

    A novel positive-polarity electrostatic precipitator (ESP) was developed using an ionization stage (0.4 × 0.4 × 0.14 m(3) ) with 16 carbon fiber ionizers in each channel and a collection stage (0.4 × 0.4 × 0.21 m(3) ) with parallel metallic plates. The single-pass collection efficiency and clean air delivery rate (CADR) were measured by standard tests using KCl particles in 0.25-0.35 μm. Performance was determined using the Deutsch equation and established diffusion and field charging theories and also compared with the commercialized HEPA filter-type air cleaner. Experimental results showed that the single-pass collection efficiency of the ESP ranged from 50 to 95% and decreased with the flow rate (10-20 m(3) /min), but increased with the voltage applied to the ionizers (6 to 8 kV) and collection plates (-5 to -7 kV). The ESP with 18 m(3) /min achieved a CADR of 12.1 m(3) /min with a voltage of 8 kV applied to the ionization stage and with a voltage of -6 kV applied to the collection stage. The concentration of ozone in the test chamber (30.4 m(3) ), a maximum value of 5.4 ppb over 12 h of continuous operation, was much lower than the current indoor regulation (50 ppb).

  11. Submicrometer particle removal indoors by a novel electrostatic precipitator with high clean air delivery rate, low ozone emissions, and carbon fiber ionizer.

    PubMed

    Kim, H-J; Han, B; Kim, Y-J; Oda, T; Won, H

    2013-10-01

    A novel positive-polarity electrostatic precipitator (ESP) was developed using an ionization stage (0.4 × 0.4 × 0.14 m(3) ) with 16 carbon fiber ionizers in each channel and a collection stage (0.4 × 0.4 × 0.21 m(3) ) with parallel metallic plates. The single-pass collection efficiency and clean air delivery rate (CADR) were measured by standard tests using KCl particles in 0.25-0.35 μm. Performance was determined using the Deutsch equation and established diffusion and field charging theories and also compared with the commercialized HEPA filter-type air cleaner. Experimental results showed that the single-pass collection efficiency of the ESP ranged from 50 to 95% and decreased with the flow rate (10-20 m(3) /min), but increased with the voltage applied to the ionizers (6 to 8 kV) and collection plates (-5 to -7 kV). The ESP with 18 m(3) /min achieved a CADR of 12.1 m(3) /min with a voltage of 8 kV applied to the ionization stage and with a voltage of -6 kV applied to the collection stage. The concentration of ozone in the test chamber (30.4 m(3) ), a maximum value of 5.4 ppb over 12 h of continuous operation, was much lower than the current indoor regulation (50 ppb). PMID:23418721

  12. Air

    MedlinePlus

    ... do to protect yourself from dirty air . Indoor air pollution and outdoor air pollution Air can be polluted indoors and it can ... this chart to see what things cause indoor air pollution and what things cause outdoor air pollution! Indoor ...

  13. SU-E-T-552: Monte Carlo Calculation of Correction Factors for a Free-Air Ionization Chamber in Support of a National Air-Kerma Standard for Electronic Brachytherapy

    SciTech Connect

    Mille, M; Bergstrom, P

    2015-06-15

    Purpose: To use Monte Carlo radiation transport methods to calculate correction factors for a free-air ionization chamber in support of a national air-kerma standard for low-energy, miniature x-ray sources used for electronic brachytherapy (eBx). Methods: The NIST is establishing a calibration service for well-type ionization chambers used to characterize the strength of eBx sources prior to clinical use. The calibration approach involves establishing the well-chamber’s response to an eBx source whose air-kerma rate at a 50 cm distance is determined through a primary measurement performed using the Lamperti free-air ionization chamber. However, the free-air chamber measurements of charge or current can only be related to the reference air-kerma standard after applying several corrections, some of which are best determined via Monte Carlo simulation. To this end, a detailed geometric model of the Lamperti chamber was developed in the EGSnrc code based on the engineering drawings of the instrument. The egs-fac user code in EGSnrc was then used to calculate energy-dependent correction factors which account for missing or undesired ionization arising from effects such as: (1) attenuation and scatter of the x-rays in air; (2) primary electrons escaping the charge collection region; (3) lack of charged particle equilibrium; (4) atomic fluorescence and bremsstrahlung radiation. Results: Energy-dependent correction factors were calculated assuming a monoenergetic point source with the photon energy ranging from 2 keV to 60 keV in 2 keV increments. Sufficient photon histories were simulated so that the Monte Carlo statistical uncertainty of the correction factors was less than 0.01%. The correction factors for a specific eBx source will be determined by integrating these tabulated results over its measured x-ray spectrum. Conclusion: The correction factors calculated in this work are important for establishing a national standard for eBx which will help ensure that dose

  14. Conception and realization of a parallel-plate free-air ionization chamber for the absolute dosimetry of an ultrasoft X-ray beam.

    PubMed

    Groetz, J-E; Ounoughi, N; Mavon, C; Belafrites, A; Fromm, M

    2014-08-01

    We report the design of a millimeter-sized parallel plate free-air ionization chamber (IC) aimed at determining the absolute air kerma rate of an ultra-soft X-ray beam (E = 1.5 keV). The size of the IC was determined so that the measurement volume satisfies the condition of charged-particle equilibrium. The correction factors necessary to properly measure the absolute kerma using the IC have been established. Particular attention was given to the determination of the effective mean energy for the 1.5 keV photons using the PENELOPE code. Other correction factors were determined by means of computer simulation (COMSOL™ and FLUKA). Measurements of air kerma rates under specific operating parameters of the lab-bench X-ray source have been performed at various distances from that source and compared to Monte Carlo calculations. We show that the developed ionization chamber makes it possible to determine accurate photon fluence rates in routine work and will constitute substantial time-savings for future radiobiological experiments based on the use of ultra-soft X-rays.

  15. Conception and realization of a parallel-plate free-air ionization chamber for the absolute dosimetry of an ultrasoft X-ray beam

    NASA Astrophysics Data System (ADS)

    Groetz, J.-E.; Ounoughi, N.; Mavon, C.; Belafrites, A.; Fromm, M.

    2014-08-01

    We report the design of a millimeter-sized parallel plate free-air ionization chamber (IC) aimed at determining the absolute air kerma rate of an ultra-soft X-ray beam (E = 1.5 keV). The size of the IC was determined so that the measurement volume satisfies the condition of charged-particle equilibrium. The correction factors necessary to properly measure the absolute kerma using the IC have been established. Particular attention was given to the determination of the effective mean energy for the 1.5 keV photons using the PENELOPE code. Other correction factors were determined by means of computer simulation (COMSOL™and FLUKA). Measurements of air kerma rates under specific operating parameters of the lab-bench X-ray source have been performed at various distances from that source and compared to Monte Carlo calculations. We show that the developed ionization chamber makes it possible to determine accurate photon fluence rates in routine work and will constitute substantial time-savings for future radiobiological experiments based on the use of ultra-soft X-rays.

  16. Conception and realization of a parallel-plate free-air ionization chamber for the absolute dosimetry of an ultrasoft X-ray beam

    SciTech Connect

    Groetz, J.-E. Mavon, C.; Fromm, M.; Ounoughi, N.; Belafrites, A.

    2014-08-15

    We report the design of a millimeter-sized parallel plate free-air ionization chamber (IC) aimed at determining the absolute air kerma rate of an ultra-soft X-ray beam (E = 1.5 keV). The size of the IC was determined so that the measurement volume satisfies the condition of charged-particle equilibrium. The correction factors necessary to properly measure the absolute kerma using the IC have been established. Particular attention was given to the determination of the effective mean energy for the 1.5 keV photons using the PENELOPE code. Other correction factors were determined by means of computer simulation (COMSOL™and FLUKA). Measurements of air kerma rates under specific operating parameters of the lab-bench X-ray source have been performed at various distances from that source and compared to Monte Carlo calculations. We show that the developed ionization chamber makes it possible to determine accurate photon fluence rates in routine work and will constitute substantial time-savings for future radiobiological experiments based on the use of ultra-soft X-rays.

  17. Comparison of Experimental and Calculated Ion Mobilities of Small Molecules in Air

    PubMed Central

    2016-01-01

    Ion mobility spectrometry is a well-known technique for analyzing gases. Examples are military applications, but also safety related applications, for example, for protection of employees in industries working with hazardous gases. In the last 15 years, this technique has been further developed as a tool for structural analysis, for example, in pharmaceutical applications. In particular, the collision cross section, which is related to the mobility, is of interest here. With help of theoretic principles, it is possible to develop molecular models that can be verified by the comparison of their calculated cross sections with experimental data. In this paper, it is analyzed how well the ion trajectory method is suitable to reproduce the measured ion mobility of small organic molecules such as the water clusters forming the positively charged reactant ions, simple aromatic substances, and n-alkanes. PMID:27298751

  18. Sensitive and comprehensive detection of chemical warfare agents in air by atmospheric pressure chemical ionization ion trap tandem mass spectrometry with counterflow introduction.

    PubMed

    Seto, Yasuo; Sekiguchi, Hiroshi; Maruko, Hisashi; Yamashiro, Shigeharu; Sano, Yasuhiro; Takayama, Yasuo; Sekioka, Ryoji; Yamaguchi, Shintaro; Kishi, Shintaro; Satoh, Takafumi; Sekiguchi, Hiroyuki; Iura, Kazumitsu; Nagashima, Hisayuki; Nagoya, Tomoki; Tsuge, Kouichiro; Ohsawa, Isaac; Okumura, Akihiko; Takada, Yasuaki; Ezawa, Naoya; Watanabe, Susumu; Hashimoto, Hiroaki

    2014-05-01

    A highly sensitive and specific real-time field-deployable detection technology, based on counterflow air introduction atmospheric pressure chemical ionization, has been developed for a wide range of chemical warfare agents (CWAs) comprising gaseous (two blood agents, three choking agents), volatile (six nerve gases and one precursor agent, five blister agents), and nonvolatile (three lachrymators, three vomiting agents) agents in air. The approach can afford effective chemical ionization, in both positive and negative ion modes, for ion trap multiple-stage mass spectrometry (MS(n)). The volatile and nonvolatile CWAs tested provided characteristic ions, which were fragmented into MS(3) product ions in positive and negative ion modes. Portions of the fragment ions were assigned by laboratory hybrid mass spectrometry (MS) composed of linear ion trap and high-resolution mass spectrometers. Gaseous agents were detected by MS or MS(2) in negative ion mode. The limits of detection for a 1 s measurement were typically at or below the microgram per cubic meter level except for chloropicrin (submilligram per cubic meter). Matrix effects by gasoline vapor resulted in minimal false-positive signals for all the CWAs and some signal suppression in the case of mustard gas. The moisture level did influence the measurement of the CWAs.

  19. Sensitive and comprehensive detection of chemical warfare agents in air by atmospheric pressure chemical ionization ion trap tandem mass spectrometry with counterflow introduction.

    PubMed

    Seto, Yasuo; Sekiguchi, Hiroshi; Maruko, Hisashi; Yamashiro, Shigeharu; Sano, Yasuhiro; Takayama, Yasuo; Sekioka, Ryoji; Yamaguchi, Shintaro; Kishi, Shintaro; Satoh, Takafumi; Sekiguchi, Hiroyuki; Iura, Kazumitsu; Nagashima, Hisayuki; Nagoya, Tomoki; Tsuge, Kouichiro; Ohsawa, Isaac; Okumura, Akihiko; Takada, Yasuaki; Ezawa, Naoya; Watanabe, Susumu; Hashimoto, Hiroaki

    2014-05-01

    A highly sensitive and specific real-time field-deployable detection technology, based on counterflow air introduction atmospheric pressure chemical ionization, has been developed for a wide range of chemical warfare agents (CWAs) comprising gaseous (two blood agents, three choking agents), volatile (six nerve gases and one precursor agent, five blister agents), and nonvolatile (three lachrymators, three vomiting agents) agents in air. The approach can afford effective chemical ionization, in both positive and negative ion modes, for ion trap multiple-stage mass spectrometry (MS(n)). The volatile and nonvolatile CWAs tested provided characteristic ions, which were fragmented into MS(3) product ions in positive and negative ion modes. Portions of the fragment ions were assigned by laboratory hybrid mass spectrometry (MS) composed of linear ion trap and high-resolution mass spectrometers. Gaseous agents were detected by MS or MS(2) in negative ion mode. The limits of detection for a 1 s measurement were typically at or below the microgram per cubic meter level except for chloropicrin (submilligram per cubic meter). Matrix effects by gasoline vapor resulted in minimal false-positive signals for all the CWAs and some signal suppression in the case of mustard gas. The moisture level did influence the measurement of the CWAs. PMID:24678766

  20. MoS2/Ag nanohybrid: A novel matrix with synergistic effect for small molecule drugs analysis by negative-ion matrix-assisted laser desorption/ionization time-of-flight mass spectrometry.

    PubMed

    Zhao, Yaju; Deng, Guoqing; Liu, Xiaohui; Sun, Liang; Li, Hui; Cheng, Quan; Xi, Kai; Xu, Danke

    2016-09-21

    This paper reports a facile synthesis of molybdenum disulfide nanosheets/silver nanoparticles (MoS2/Ag) hybrid and its use as an effective matrix in negative ion matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS). The nanohybrid exerts a strong synergistic effect, leading to high performance detection of small molecule analytes including amino acids, peptides, fatty acids and drugs. The enhancement of laser desorption/ionization (LDI) efficiency is largely attributed to the high surface roughness and large surface area for analyte adsorption, better dispersibility, increased thermal conductivity and enhanced UV energy absorption as compared to pure MoS2. Moreover, both Ag nanoparticles and the edge of the MoS2 layers function as deprotonation sites for proton capture, facilitating the charging process in negative ion mode and promoting formation of negative ions. As a result, the MoS2/Ag nanohybrid proves to be a highly attractive matrix in MALDI-TOF MS, with desired features such as high desorption/ionization efficiency, low fragmentation interference, high salt tolerance, and no sweet-spots for mass signal. These characteristic properties allowed for simultaneous analysis of eight different drugs and quantification of acetylsalicylic acid in the spiked human serum. This work demonstrates for the first time the fabrication and application of a novel MoS2/Ag hybrid, and provides a new platform for use in the rapid and high throughput analysis of small molecules by mass spectrometry.

  1. MoS2/Ag nanohybrid: A novel matrix with synergistic effect for small molecule drugs analysis by negative-ion matrix-assisted laser desorption/ionization time-of-flight mass spectrometry.

    PubMed

    Zhao, Yaju; Deng, Guoqing; Liu, Xiaohui; Sun, Liang; Li, Hui; Cheng, Quan; Xi, Kai; Xu, Danke

    2016-09-21

    This paper reports a facile synthesis of molybdenum disulfide nanosheets/silver nanoparticles (MoS2/Ag) hybrid and its use as an effective matrix in negative ion matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS). The nanohybrid exerts a strong synergistic effect, leading to high performance detection of small molecule analytes including amino acids, peptides, fatty acids and drugs. The enhancement of laser desorption/ionization (LDI) efficiency is largely attributed to the high surface roughness and large surface area for analyte adsorption, better dispersibility, increased thermal conductivity and enhanced UV energy absorption as compared to pure MoS2. Moreover, both Ag nanoparticles and the edge of the MoS2 layers function as deprotonation sites for proton capture, facilitating the charging process in negative ion mode and promoting formation of negative ions. As a result, the MoS2/Ag nanohybrid proves to be a highly attractive matrix in MALDI-TOF MS, with desired features such as high desorption/ionization efficiency, low fragmentation interference, high salt tolerance, and no sweet-spots for mass signal. These characteristic properties allowed for simultaneous analysis of eight different drugs and quantification of acetylsalicylic acid in the spiked human serum. This work demonstrates for the first time the fabrication and application of a novel MoS2/Ag hybrid, and provides a new platform for use in the rapid and high throughput analysis of small molecules by mass spectrometry. PMID:27590549

  2. Synergistic effect of graphene oxide/MWCNT films in laser desorption/ionization mass spectrometry of small molecules and tissue imaging.

    PubMed

    Kim, Young-Kwan; Na, Hee-Kyung; Kwack, Sul-Jin; Ryoo, Soo-Ryoon; Lee, Youngmi; Hong, Seunghee; Hong, Sungwoo; Jeong, Yong; Min, Dal-Hee

    2011-06-28

    Matrix-assisted laser desorption/ionization mass spectrometry has been considered an important tool for various biochemical analyses and proteomics research. Although addition of conventional matrix efficiently supports laser desorption/ionization of analytes with minimal fragmentation, it often results in high background interference and misinterpretation of the spatial distribution of biomolecules especially in low-mass regions. Here, we show design, systematic characterization, and application of graphene oxide/multiwalled carbon nanotube-based films fabricated on solid substrates as a new matrix-free laser desorption/ionization platform. We demonstrate that the graphene oxide/multiwalled carbon nanotube double layer provides many advantages as a laser desorption/ionization substrate, such as efficient desorption/ionization of analytes with minimum fragmentation, high salt tolerance, no sweet-spots for mass signal, excellent durability against mechanical and photoagitation and prolonged exposure to ambient conditions, and applicability to tissue imaging mass spectrometry. This platform will be widely used as an important tool for mass spectrometry-based biochemical analyses because of its outstanding performance, long-term stability, and cost effectiveness.

  3. Direct measurement of air kerma rate in air from CDCS J-type caesium-137 therapy sources using a Farmer ionization chamber.

    PubMed

    Poynter, A J

    2000-04-01

    A simple method for directly measuring the reference air kerma rate from J-type 137Cs sources using a Farmer 2571 chamber has been evaluated. The method is useful as an independent means of verifying manufacturers' test data.

  4. Analytical method validation for the determination of 2,3,3,3-tetrafluoropropene in air samples using gas chromatography with flame ionization detection.

    PubMed

    Mawn, Michael P; Kurtz, Kristine; Stahl, Deborah; Chalfant, Richard L; Koban, Mary E; Dawson, Barbara J

    2013-01-01

    A new low global warming refrigerant, 2,3,3,3-tetrafluoro propene, or HFO-1234yf, has been successfully evaluated for automotive air conditioning, and is also being evaluated for stationary refrigeration and air conditioning systems. Due to the advantageous environmental properties of HFO-1234yf versus HFC-134a, coupled with its similar physical properties and system performance, HFO-1234yf is also being evaluated to replace HFC-134a in refrigeration applications where neat HFC-134a is currently used. This study reports on the development and validation of a sampling and analytical method for the determination of HFO-1234yf in air. Different collection media were screened for desorption and simulated sampling efficiency with three-section (350/350/350 mg) Anasorb CSC showing the best results. Therefore, air samples were collected using two 3-section Anasorb CSC sorbent tubes in series at 0.02 L/min for up to 8 hr for sample volumes of up to 9.6 L. The sorbent tubes were extracted in methylene chloride, and analyzed by gas chromatography with flame ionization detection. The method was validated from 0.1× to 20× the target level of 0.5 ppm (2.3 mg/m(3)) for a 9.6 L air volume. Desorption efficiencies for HFO-1234yf were 88 to 109% for all replicates over the validation range with a mean overall recovery of 93%. Simulated sampling efficiencies ranged from 87 to 104% with a mean of 94%. No migration or breakthrough to the back tube was observed under the sampling conditions evaluated. HFO-1234yf samples showed acceptable storage stability on Anasorb CSC sorbent up to a period of 30 days when stored under ambient, refrigerated, or frozen temperature conditions.

  5. CuFe2O4 magnetic nanocrystal clusters as a matrix for the analysis of small molecules by negative-ion matrix-assisted laser desorption/ionization time-of-flight mass spectrometry.

    PubMed

    Lin, Zian; Zheng, Jiangnan; Bian, Wei; Cai, Zongwei

    2015-08-01

    CuFe2O4 magnetic nanocrystal clusters (CuFe2O4 MNCs) were proposed as a new matrix for small molecule analysis by negative ion matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) for the first time. We demonstrated its advantages over conventional organic matrices in the detection of small molecules such as amino acids, peptides, nucleobases, fatty acids, and steroid hormones. A systematic comparison of CuFe2O4 MNCs with different ionization modes revealed that MS spectra obtained for the CuFe2O4 MNC matrix in the negative ion mode was only featured by deprotonated ion peaks with a free matrix background, which was different from the complicated alkali metal adducts produced in the positive ion mode. The developed method was found relatively tolerant to salt contamination and exhibited good reproducibility. A detection limit down to the subpicomolar level was achieved when testosterone was analyzed. In addition, by comparison of the MS spectra obtained from bare Fe3O4 and MFe2O4 MNC (M = Co, Ni, Cu, Zn) matrices, two main factors of MFe2O4 MNC matrices were revealed to play a vital role in assisting the negative ion desorption/ionization (D/I) process: doping transition metals into ferrite nanocrystals favoring laser absorption and energy transfer and a good match between the UV absorption of MFe2O4 MNCs and the excitation of nitrogen laser source facilitating LDI efficiency. This work creates a new branch of application for MFe2O4 MNCs and provides an alternative solution for small molecule analysis. PMID:26086699

  6. Microplasma Ionization of Volatile Organics for Improving Air/Water Monitoring Systems On-Board the International Space Station.

    PubMed

    Bernier, Matthew C; Alberici, Rosana M; Keelor, Joel D; Dwivedi, Prabha; Zambrzycki, Stephen C; Wallace, William T; Gazda, Daniel B; Limero, Thomas F; Symonds, Josh M; Orlando, Thomas M; Macatangay, Ariel; Fernández, Facundo M

    2016-07-01

    Low molecular weight polar organics are commonly observed in spacecraft environments. Increasing concentrations of one or more of these contaminants can negatively impact Environmental Control and Life Support (ECLS) systems and/or the health of crew members, posing potential risks to the success of manned space missions. Ambient plasma ionization mass spectrometry (MS) is finding effective use as part of the analytical methodologies being tested for next-generation space module environmental analysis. However, ambient ionization methods employing atmospheric plasmas typically require relatively high operation voltages and power, thus limiting their applicability in combination with fieldable mass spectrometers. In this work, we investigate the use of a low power microplasma device in the microhollow cathode discharge (MHCD) configuration for the analysis of polar organics encountered in space missions. A metal-insulator-metal (MIM) structure with molybdenum foil disc electrodes and a mica insulator was used to form a 300 μm diameter plasma discharge cavity. We demonstrate the application of these MIM microplasmas as part of a versatile miniature ion source for the analysis of typical volatile contaminants found in the International Space Station (ISS) environment, highlighting their advantages as low cost and simple analytical devices. Graphical Abstract ᅟ.

  7. Microplasma Ionization of Volatile Organics for Improving Air/Water Monitoring Systems On-Board the International Space Station

    NASA Astrophysics Data System (ADS)

    Bernier, Matthew C.; Alberici, Rosana M.; Keelor, Joel D.; Dwivedi, Prabha; Zambrzycki, Stephen C.; Wallace, William T.; Gazda, Daniel B.; Limero, Thomas F.; Symonds, Josh M.; Orlando, Thomas M.; Macatangay, Ariel; Fernández, Facundo M.

    2016-07-01

    Low molecular weight polar organics are commonly observed in spacecraft environments. Increasing concentrations of one or more of these contaminants can negatively impact Environmental Control and Life Support (ECLS) systems and/or the health of crew members, posing potential risks to the success of manned space missions. Ambient plasma ionization mass spectrometry (MS) is finding effective use as part of the analytical methodologies being tested for next-generation space module environmental analysis. However, ambient ionization methods employing atmospheric plasmas typically require relatively high operation voltages and power, thus limiting their applicability in combination with fieldable mass spectrometers. In this work, we investigate the use of a low power microplasma device in the microhollow cathode discharge (MHCD) configuration for the analysis of polar organics encountered in space missions. A metal-insulator-metal (MIM) structure with molybdenum foil disc electrodes and a mica insulator was used to form a 300 μm diameter plasma discharge cavity. We demonstrate the application of these MIM microplasmas as part of a versatile miniature ion source for the analysis of typical volatile contaminants found in the International Space Station (ISS) environment, highlighting their advantages as low cost and simple analytical devices.

  8. Microplasma Ionization of Volatile Organics for Improving Air/Water Monitoring Systems On-Board the International Space Station.

    PubMed

    Bernier, Matthew C; Alberici, Rosana M; Keelor, Joel D; Dwivedi, Prabha; Zambrzycki, Stephen C; Wallace, William T; Gazda, Daniel B; Limero, Thomas F; Symonds, Josh M; Orlando, Thomas M; Macatangay, Ariel; Fernández, Facundo M

    2016-07-01

    Low molecular weight polar organics are commonly observed in spacecraft environments. Increasing concentrations of one or more of these contaminants can negatively impact Environmental Control and Life Support (ECLS) systems and/or the health of crew members, posing potential risks to the success of manned space missions. Ambient plasma ionization mass spectrometry (MS) is finding effective use as part of the analytical methodologies being tested for next-generation space module environmental analysis. However, ambient ionization methods employing atmospheric plasmas typically require relatively high operation voltages and power, thus limiting their applicability in combination with fieldable mass spectrometers. In this work, we investigate the use of a low power microplasma device in the microhollow cathode discharge (MHCD) configuration for the analysis of polar organics encountered in space missions. A metal-insulator-metal (MIM) structure with molybdenum foil disc electrodes and a mica insulator was used to form a 300 μm diameter plasma discharge cavity. We demonstrate the application of these MIM microplasmas as part of a versatile miniature ion source for the analysis of typical volatile contaminants found in the International Space Station (ISS) environment, highlighting their advantages as low cost and simple analytical devices. Graphical Abstract ᅟ. PMID:27080004

  9. Ionization probes of molecular structure and chemistry

    SciTech Connect

    Johnson, P.M.

    1993-12-01

    Various photoionization processes provide very sensitive probes for the detection and understanding of the spectra of molecules relevant to combustion processes. The detection of ionization can be selective by using resonant multiphoton ionization or by exploiting the fact that different molecules have different sets of ionization potentials. Therefore, the structure and dynamics of individual molecules can be studied even in a mixed sample. The authors are continuing to develop methods for the selective spectroscopic detection of molecules by ionization, and to use these methods for the study of some molecules of combustion interest.

  10. Characteristics of a miniature parallel-plate free-air ionization chamber for measuring the intensity of synchrotron radiation from an undulator

    NASA Astrophysics Data System (ADS)

    Nariyama, Nobuteru

    2004-09-01

    In order to develop an absolute intensity monitor for synchrotron radiation from an undulator, the characteristics of a parallel-plate free-air ionization chamber with a plate separation of 4.2 mm, which was considered to be as narrow as possible, were investigated using 8-30 keV monoenergetic photons at SPring-8. Using a Si-PIN photodiode as the reference monitor, saturation was confirmed at 8-30 keV at a photon intensity of an order of 1013 photons/s. The collection efficiency became almost unity at 8 and 10 keV within 3.8% and 1.1%, respectively, which gradually decreased with increasing energy and attained 0.52 at 30 keV because some of the high-energy electrons escaped from the sensitive volume. When the pair of electrodes was transferred from the upper and lower sides to the left and right sides of the beam axis in order to investigate the influence of linear polarization of synchrotron radiation, a decrease in the collection efficiency was observed. Monte Carlo simulations considering linear polarization showed that the plate separation required for no electron loss was 26, 14, and 8 mm for 30, 20, and 15 keV photons, respectively. For 20 keV photons, saturation characteristics were investigated using an ionization chamber with 14 mm plate separation.

  11. Infrared and reflectron time-of-flight mass spectroscopic analysis of methane (CH4)-carbon monoxide (CO) ices exposed to ionization radiation--toward the formation of carbonyl-bearing molecules in extraterrestrial ices.

    PubMed

    Kaiser, Ralf I; Maity, Surajit; Jones, Brant M

    2014-02-28

    Ice mixtures of methane and carbon monoxide were exposed to ionizing radiation in the form of energetic electrons at 5.5 K to investigate the formation of carbonyl bearing molecules in extraterrestrial ices. The radiation induced chemical processing of the mixed ices along with their isotopically labeled counterparts was probed online and in situ via infrared spectroscopy (solid state) aided with reflectron time-of-flight mass spectrometry (ReTOFMS) coupled to single photon photoionization (PI) at 10.49 eV (gas phase). Deconvolution of the carbonyl absorption feature centered at 1727 cm(-1) in the processed ices and subsequent kinetic fitting to the temporal growth of the newly formed species suggests the formation of acetaldehyde (CH3CHO) together with four key classes of carbonyl-bearing molecules: (i) alkyl aldehydes, (ii) alkyl ketones, (iii) α,β-unsaturated ketones/aldehydes and (iv) α,β,γ,δ-unsaturated ketones/α,β-dicarbonyl compounds in keto-enol form. The mechanistical studies indicate that acetaldehyde acts as the key building block of higher aldehydes (i) and ketones (ii) with unsaturated ketones/aldehydes (iii) and/or α,β-dicarbonyl compounds (iv) formed from the latter. Upon sublimation of the newly synthesized molecules, ReTOFMS together with isotopic shifts of the mass-to-charge ratios was exploited to identify eleven product classes containing molecules with up to six carbon atoms, which can be formally derived from C1-C5 hydrocarbons incorporating up to three carbon monoxide building blocks. The classes are (i) saturated aldehydes/ketones, (ii) unsaturated aldehydes/ketones, (iii) doubly unsaturated aldehydes/ketones, (iv) saturated dicarbonyls (aldehydes/ketones), (v) unsaturated dicarbonyls (aldehydes/ketones), (vi) saturated tricarbonyls (aldehydes/ketones), molecules containing (vii) one carbonyl - one alcohol (viii), two carbonyls - one alcohol, (ix) one carbonyl - two alcohol groups along with (x) alcohols and (xi) diols. Reaction

  12. Ionizing radiation induces structural and functional damage on the molecules of rat brain homogenate membranes: a Fourier transform infrared (FT-IR) spectroscopic study.

    PubMed

    Demir, Pinar; Akkas, Sara B; Severcan, Mete; Zorlu, Faruk; Severcan, Feride

    2015-01-01

    Humans can be exposed to ionizing radiation, due to various reasons, whose structural effects on biological membranes are not well defined. The current study aims to understand the ionizing radiation-induced structural and functional alterations in biomolecules of brain membranes using Fourier transform infrared (FT-IR) spectroscopy using rat animal models. For this purpose, 1000 cGy of ionizing radiation was specifically directed to the head of Sprague Dawley rats. The rats were decapitated after 24 h. The results revealed that the lipid-to-protein ratio decreased and that irradiation caused lipid peroxidation and increases in the amounts of olefinic =CH, carbonyl, and methylene groups of lipids. In addition, ionizing radiation induced a decrease in membrane fluidity, disordering of membrane lipids, strengthening of the hydrogen bonding of the phosphate groups of lipid head-groups, and weakening in the hydrogen bonding of the interfacial carbonyl groups of lipids. Radiation further caused significant decrements in the α-helix and turns, and significant increments in the β-sheet and random coil contents in the protein structure. Hierarchical cluster analyses, performed in the whole region (3030-1000 cm(-1)), lipid (3030-2800 cm(-1)), and protein (1700-1600 cm(-1)) regions separately, successfully differentiated the control and irradiated groups of rat brain membranes and showed that proteins in the membranes are affected more than lipids from the damages induced with ionizing radiation. As a result, the current study showed that FT-IR spectroscopy can be used successfully as a novel method to monitor radiation-induced alterations on biological membranes.

  13. Abnormal ionization in sonoluminescence

    NASA Astrophysics Data System (ADS)

    Zhang, Wen-Juan; An, Yu

    2015-04-01

    Sonoluminescence is a complex phenomenon, the mechanism of which remains unclear. The present study reveals that an abnormal ionization process is likely to be present in the sonoluminescing bubble. To fit the experimental data of previous studies, we assume that the ionization energies of the molecules and atoms in the bubble decrease as the gas density increases and that the decrease of the ionization energy reaches about 60%-70% as the bubble flashes, which is difficult to explain by using previous models. Project supported by the Research Fund for the Doctoral Program of Higher Education of China (Grant No. 20120002110031) and the National Natural Science Foundation of China (Grant No. 11334005).

  14. Multi-concentric-ring open-air ionization chamber for high-intensity X-ray beams

    NASA Astrophysics Data System (ADS)

    Nariyama, Nobuteru

    2014-11-01

    An ionization chamber with four concentric ring electrodes was used to measure doses of white, 10, 15 and 20 keV synchrotron X-ray beams. The ring-shaped electrodes, which had diameters less than 11.8 mm, collected charges independently only around the beam, excluding strong in-beam charges when the beams passed through a small hole in the electrode centers. As a result, under low saturation voltages, the measured dose rates were confirmed to correlate with the beam intensity when conversion factors calculated with a Monte Carlo code were employed. The influence of the assumed beam sizes and incident positions on the current was almost negligible, with the exception of the incident position dependence at 10 keV.

  15. Monitoring of Hazardous Air Pollutant Surrogates Using Resonance Enhanced Multiphoton Ionization/Time of Flight Mass Spectrometry

    EPA Science Inventory

    EPA’s preferred approach for regulatory emissions compliance is based upon real-time monitoring of individual hazardous air pollutants (HAPs). Real-time, continuous monitoring not only provides the most comprehensive assurance of emissions compliance, but also can serve as...

  16. Determination of Hazardous Air Pollutant Surrogates Using Resonance Enhanced Multi Photon Ionization - Time of Flight Mass Spectrometry

    EPA Science Inventory

    EPA?s preferred approach for regulatory emissions compliance is based upon real-time monitoring of individual hazardous air pollutants (HAPs). Real-time, continuous monitoring not only provides the most comprehensive assurance of emissions compliance, but also can serve as a pro...

  17. Effects of Post-Pyrolysis Air Oxidation of Biomass Chars on Adsorption of Neutral and Ionizable Compounds.

    PubMed

    Xiao, Feng; Pignatello, Joseph J

    2016-06-21

    This study was conducted to understand the effects of thermal air oxidation of biomass chars experienced during formation or production on their adsorptive properties toward various compounds, including five neutral nonpolar and polar compounds and seven weak acids and bases (pKa = 3-5.2) selected from among industrial chemicals and the triazine and phenoxyacetic acid herbicide classes. Post-pyrolysis air oxidation (PPAO) at 400 °C of anoxically prepared wood and pecan shell chars for up to 40 min enhanced the mass-normalized adsorption at pH ∼ 7.4 of all test compounds, especially the weak acids and bases, by up to 100-fold. Both general and specific effects were identified. The general effect results from "reaming" of pores by the oxidative removal of pore wall matter and/or tarry deposits generated during the pyrolysis step. Reaming creates new surface area and enlarges nanopores, which helps relieve steric hindrance to adsorption. The specific effect results from creation of new acidic functionality that provides sites for the formation of very strong, charge-assisted hydrogen bonds (CAHB) with solutes having comparable pKa. The CAHB hypothesis was supported by competition experiments and the finding that weak acid anion adsorption increased with surface carboxyl content, despite electrostatic repulsion from the growing negative charge. The results provide insight into the effects of air oxidation on pollutant retention. PMID:27152745

  18. A Novel Small-Molecule Compound of Lithium Iodine and 3-Hydroxypropionitride as a Solid-State Electrolyte for Lithium-Air Batteries.

    PubMed

    Liu, Fang-Chao; Shadike, Zulipiya; Wang, Xiao-Fang; Shi, Si-Qi; Zhou, Yong-Ning; Chen, Guo-Ying; Yang, Xiao-Qing; Weng, Lin-Hong; Zhao, Jing-Tai; Fu, Zheng-Wen

    2016-07-01

    A novel small-molecule compound of lithium iodine and 3-hydroxypropionitrile (HPN) has been successfully synthesized. Our combined experimental and theoretical studies indicated that LiIHPN is a Li-ion conductor, which is utterly different from the I(-)-anion conductor of LiI(HPN)2 reported previously. Solid-state lithium-air batteries based on LiIHPN as the electrolyte exhibit a reversible discharge capacity of more than 2100 mAh g(-1) with a cyclic performance over 10 cycles. Our findings provide a new way to design solid-state electrolytes toward high-performance lithium-air batteries. PMID:27308962

  19. A novel small-molecule compound of lithium iodine and 3-hydroxypropionitride as a solid-state electrolyte for lithium–air batteries

    DOE PAGES

    Liu, Fang -Chao; Shadike, Zulipiya; Wang, Xiao -Fang; Shi, Si -Qi; Zhou, Yong -Ning; Chen, Guo -Ying; Yang, Xiao -Qing; Weng, Lin -Hong; Zhao, Jing -Tai; Fu, Zheng -Wen

    2016-06-16

    A novel small-molecule compound of lithium iodine and 3-hydroxypropionitrile (HPN) has been successfully synthesized. Our combined experimental and theoretical studies indicated that LiIHPN is a Li-ion conductor, which is utterly different from the I–-anion conductor of LiI(HPN)2 reported previously. Solid-state lithium–air batteries based on LiIHPN as the electrolyte exhibit a reversible discharge capacity of more than 2100 mAh g–1 with a cyclic performance over 10 cycles. Lastly, our findings provide a new way to design solid-state electrolytes toward high-performance lithium–air batteries.

  20. Comparing Coulomb explosion dynamics of multiply charged triatomic molecules after ionization by highly charged ion impact and few cycle femtosecond laser pulses

    NASA Astrophysics Data System (ADS)

    Wales, B.; Karimi, R.; Bisson, E.; Beaulieu, S.; Giguère, M.; Motojima, T.; Anderson, R.; Matsumoto, J.; Kieffer, J.-C.; Légaré, F.; Shiromaru, H.; Sanderson, J.

    2013-09-01

    Recent experiments using highly charged ions (HCI) at Tokyo Metropolitan University and few cycle laser pulses at the advanced laser light source have centered on multiply ionizing carbonyl sulfide to form charge states from 3 + to 7 + . By measuring the kinetic energy release during subsequent break up and comparing with previous results from HCI impact on CO2 we can see a pattern emerging which implies that shorter laser pulses than the current sub 7 fs standard could lead to higher kinetic energy release than expected from Coulomb explosion.

  1. Direct analysis of samples by mass spectrometry: From elements to bio-molecules using laser ablation inductively couple plasma mass spectrometry and laser desorption/ionization mass spectrometry

    SciTech Connect

    Perdian, David C.

    2009-01-01

    Mass spectrometric methods that are able to analyze solid samples or biological materials with little or no sample preparation are invaluable to science as well as society. Fundamental research that has discovered experimental and instrumental parameters that inhibit fractionation effects that occur during the quantification of elemental species in solid samples by laser ablation inductively coupled plasma mass spectrometry is described. Research that determines the effectiveness of novel laser desorption/ionization mass spectrometric methods for the molecular analysis of biological tissues at atmospheric pressure and at high spatial resolution is also described. A spatial resolution is achieved that is able to analyze samples at the single cell level.

  2. Cyclodextrin-supported organic matrix for application of MALDI-MS for forensics. Soft-ionization to obtain protonated molecules of low molecular weight compounds

    NASA Astrophysics Data System (ADS)

    Yonezawa, Tetsu; Asano, Takashi; Fujino, Tatsuya; Nishihara, Hiroshi

    2013-06-01

    A mass measurement technique for detecting low-molecular-weight drugs with a cyclodextrin-supported organic matrix was investigated. By using cyclodextrin-supported 2,4,6-trihydroxyacetophenone (THAP), the matrix-related peaks of drugs were suppressed. The peaks of protonated molecules of the sample and THAP were mainly observed, and small fragments were detected in a few cases. Despite the Na+ and K+ peaks were observed in the spectrum, Na+ or K+ adduct sample molecules were undetected, owing to the sugar units of cyclodextrin. The advantages of MALDI-MS with cyclodextrin-supported matrices as an analytical tool for forensic samples are discussed. The suppression of alkali adducted molecules and desorption process are also discussed.

  3. Tris(3-hydroxypropyl)phosphine (THPP): A mild, air-stable reagent for the rapid, reductive cleavage of small-molecule disulfides.

    PubMed

    McNulty, James; Krishnamoorthy, Venkatesan; Amoroso, Dino; Moser, Michael

    2015-10-01

    Tris(3-hydroxypropyl)phosphine (THPP) is demonstrated to be a versatile, water-soluble and air-stable reducing agent, allowing for the rapid, irreversible reductive cleavage of disulfide bonds in both aqueous and buffered aqueous-organic media. The reagent shows exceptional stability at biological pH under which condition it permits the rapid reduction of a wide range of differentially functionalized small-molecule disulfides. PMID:26318995

  4. A Cofacially Stacked Electron-Deficient Small Molecule with a High Electron Mobility of over 10 cm(2) V(-1) s(-1) in Air.

    PubMed

    Dou, Jin-Hu; Zheng, Yu-Qing; Yao, Ze-Fan; Lei, Ting; Shen, Xingxing; Luo, Xu-Yi; Yu, Zhi-Ao; Zhang, Shi-Ding; Han, Guangchao; Wang, Zhi; Yi, Yuanping; Wang, Jie-Yu; Pei, Jian

    2015-12-22

    A strong, electron-deficient small molecule, F4 -BDOPV, has a lowest unoccupied molecular orbital (LUMO) level down to -4.44 eV and exhibits cofacial packing in single crystals. These features provide F4 -BDOPV with good ambient stability and large charge-transfer integrals for electrons, leading to a high electron mobility of up to 12.6 cm(2) V(-1) s(-1) in air.

  5. Resonance-enhanced two-photon ionization mass spectroscopy of ephedrine: Indication for a state-selective fragmentation in a flexible molecule

    NASA Astrophysics Data System (ADS)

    Karaminkov, R.; Chervenkov, S.; Härter, P.; Neusser, H. J.

    2007-07-01

    The vibronic structure of the S 1 ← S 0 spectrum of ephedrine was measured by resonance-enhanced two-photon ionization spectroscopy with mass resolution under cold molecular beam conditions. The spectra recorded at four different mass channels, m/ z = 165 (parent), 58, and the hitherto unknown 71, 85 fragment ions show dissimilar vibronic fine structure and the observed mass pattern strongly depends on the selected intermediate vibrational state. This points to an intermediate state-selected process resulting in a different fragmentation mass pattern. Ab initio calculations at the MP2/6-311++G ∗∗ level demonstrate that the AG (a) conformer is more stable by 238 cm -1 than the next stable GG (a) conformer.

  6. Soft-landing ion mobility of silver clusters for small-molecule matrix-assisted laser desorption ionization mass spectrometry and imaging of latent fingerprints.

    PubMed

    Walton, Barbara L; Verbeck, Guido F

    2014-08-19

    Matrix-assisted laser desorption ionization (MALDI) imaging is gaining popularity, but matrix effects such as mass spectral interference and damage to the sample limit its applications. Replacing traditional matrices with silver particles capable of equivalent or increased photon energy absorption from the incoming laser has proven to be beneficial for low mass analysis. Not only can silver clusters be advantageous for low mass compound detection, but they can be used for imaging as well. Conventional matrix application methods can obstruct samples, such as fingerprints, rendering them useless after mass analysis. The ability to image latent fingerprints without causing damage to the ridge pattern is important as it allows for further characterization of the print. The application of silver clusters by soft-landing ion mobility allows for enhanced MALDI and preservation of fingerprint integrity.

  7. Interplay of strong chemical bonds and the repulsive Coulomb force in the metastable states of triply ionized homonuclear molecules: A theoretical study of N23+ and O23+

    NASA Astrophysics Data System (ADS)

    Imamura, Yutaka; Hatsui, Takaki

    2012-01-01

    We have studied metastable electronic states of trication molecules for N23+ and O23+ using the internally contracted multireference configuration interaction method with single and double excitations (icMRCISD). The metastable ground state for O23+ and metastable excited state for N23+ were obtained with the barriers of approximately 1.5 and 13.0 kcal/mol, respectively, although those metastable states were not found in previous calculations. The analysis on occupation numbers of natural orbitals demonstrates that the two metastable states are formed owing to the balance between the reduction of cationic Coulomb repulsion and the weakening of the chemical bonds. We have proposed to measure these metastable states by short-wavelength free-electron lasers (sFELs) that have the potential to produce excited states of multiply charged molecules.

  8. Simultaneous derivatization and air-assisted liquid-liquid microextraction of some parabens in personal care products and their determination by GC with flame ionization detection.

    PubMed

    Farajzadeh, Mir Ali; Khosrowshahi, Elnaz Marzi; Khorram, Parisa

    2013-11-01

    A simultaneous derivatization/air-assisted liquid-liquid microextraction technique has been developed for the sample pretreatment of some parabens in aqueous samples. The analytes were derivatized and extracted simultaneously by a fast reaction/extraction with butylchloroformate (derivatization agent/extraction solvent) from the aqueous samples and then analyzed by GC with flame ionization detection. The effect of catalyst type and volume, derivatization agent/extraction solvent volume, ionic strength of aqueous solution, pH, numbers of extraction, aqueous sample volume, etc. on the method efficiency was investigated. Calibration graphs were linear in the range of 2-5000 μg/L with squared correlation coefficients >0.990. Enhancement factors and enrichment factors ranged from 1535 to 1941 and 268 to 343, respectively. Detection limits were obtained in the range of 0.41-0.62 μg/L. The RSDs for the extraction and determination of 250 μg/L of each paraben were <4.9% (n = 6). In this method, the derivatization agent and extraction solvent were the same and there is no need for a dispersive solvent, which is common in a traditional dispersive liquid-liquid microextraction technique. Furthermore, the sample preparation time is very short.

  9. First-principle interaction potentials for metastable He(3S) and Ne(3P) with closed-shell molecules: application to Penning-ionizing systems.

    PubMed

    Hapka, Michał; Chałasiński, Grzegorz; Kłos, Jacek; Zuchowski, Piotr S

    2013-07-01

    We present new interaction potential curves, calculated from first-principles, for the He((3)S, 1s(1)2s(1))···H2 and He((3)S)···Ar systems, relevant in recent Penning ionization experiments of Henson et al. [Science 338, 234 (2012)]. Two different approaches were applied: supermolecular using coupled cluster (CC) theory and perturbational within symmetry-adapted perturbation theory (SAPT). Both methods gave consistent results, and the potentials were used to study the elastic scattering and determine the positions of shape resonances for low kinetic energy (up to 1 meV). We found a good agreement with the experiment. In addition, we investigated two other dimers composed of metastable Ne ((3)P, 2p(5)3s(1)) and ground state He and Ar atoms. For the Ne((3)P)···He system, a good agreement between CC and SAPT approaches was obtained. The Ne((3)P)···Ar dimer was described only with SAPT, as CC gave divergent results. Ne* systems exhibit extremely small electronic orbital angular momentum anisotropy of the potentials. We attribute this effect to screening of an open 2p shell by a singly occupied 3s shell.

  10. Accurate Ionization Potentials and Electron Affinities of Acceptor Molecules I. Reference Data at the CCSD(T) Complete Basis Set Limit.

    PubMed

    Richard, Ryan M; Marshall, Michael S; Dolgounitcheva, O; Ortiz, J V; Brédas, Jean-Luc; Marom, Noa; Sherrill, C David

    2016-02-01

    In designing organic materials for electronics applications, particularly for organic photovoltaics (OPV), the ionization potential (IP) of the donor and the electron affinity (EA) of the acceptor play key roles. This makes OPV design an appealing application for computational chemistry since IPs and EAs are readily calculable from most electronic structure methods. Unfortunately reliable, high-accuracy wave function methods, such as coupled cluster theory with single, double, and perturbative triples [CCSD(T)] in the complete basis set (CBS) limit are too expensive for routine applications to this problem for any but the smallest of systems. One solution is to calibrate approximate, less computationally expensive methods against a database of high-accuracy IP/EA values; however, to our knowledge, no such database exists for systems related to OPV design. The present work is the first of a multipart study whose overarching goal is to determine which computational methods can be used to reliably compute IPs and EAs of electron acceptors. This part introduces a database of 24 known organic electron acceptors and provides high-accuracy vertical IP and EA values expected to be within ±0.03 eV of the true non-relativistic, vertical CCSD(T)/CBS limit. Convergence of IP and EA values toward the CBS limit is studied systematically for the Hartree-Fock, MP2 correlation, and beyond-MP2 coupled cluster contributions to the focal point estimates. PMID:26731487

  11. A selected ion flow tube study of the reactions of NO + and O + 2 ions with some organic molecules: The potential for trace gas analysis of air

    NASA Astrophysics Data System (ADS)

    Španěl, Patrik; Smith, David

    1996-02-01

    A study has been carried out using our selected ion flow tube apparatus of the reactions of NO+ and O+2 ions in their vibronic ground states with ten organic species: the hydrocarbons, benzene, toluene, isoprene, cyclopropane, and n-pentane; the oxygen-containing organics, methanol, ethanol, acetaldehyde, acetone, and diethyl ether. The major objectives of this work are, on the one hand, to fully understand the processes involved in these reactions and, on the other hand, to explore the potential of NO+ and O+2 as chemical ionization agents for the analysis of trace gases in air and on human breath. Amongst the NO+ reactions, charge transfer, hydride-ion transfer, and termolecular association occur, and the measured rate coefficients, k, for the reactions vary from immeasurably small to the maximum value, collisional rate coefficient, kc. The O+2 reactions are all fast, in each case the k being equal to or an appreciable fraction of kc, and charge transfer producing the parent organic ion or dissociative charge transfer resulting in two or three fragments of the parent ion are the reaction processes that occur. We conclude from these studies, and from previous studies, that NO+ ions and O+2 ions can be used to great effect as chemical ionization agents for trace gas analysis, especially in combination with H3O+ ions which we now routinely use for this purpose.

  12. "Magic" Ionization Mass Spectrometry.

    PubMed

    Trimpin, Sarah

    2016-01-01

    The systematic study of the temperature and pressure dependence of matrix-assisted ionization (MAI) led us to the discovery of the seemingly impossible, initially explained by some reviewers as either sleight of hand or the misinterpretation by an overzealous young scientist of results reported many years before and having little utility. The “magic” that we were attempting to report was that with matrix assistance, molecules, at least as large as bovine serum albumin (66 kDa), are lifted into the gas phase as multiply charged ions simply by exposure of the matrix:analyte sample to the vacuum of a mass spectrometer. Applied heat, a laser, or voltages are not necessary to achieve charge states and ion abundances only previously observed with electrospray ionization (ESI). The fundamentals of how solid phase volatile or nonvolatile compounds are converted to gas-phase ions without added energy currently involves speculation providing a great opportunity to rethink mechanistic understanding of ionization processes used in mass spectrometry. Improved understanding of the mechanism(s) of these processes and their connection to ESI and matrix-assisted laser desorption/ionization may provide opportunities to further develop new ionization strategies for traditional and yet unforeseen applications of mass spectrometry. This Critical Insights article covers developments leading to the discovery of a seemingly magic ionization process that is simple to use, fast, sensitive, robust, and can be directly applied to surface characterization using portable or high performance mass spectrometers. PMID:26486514

  13. "Magic" Ionization Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Trimpin, Sarah

    2016-01-01

    The systematic study of the temperature and pressure dependence of matrix-assisted ionization (MAI) led us to the discovery of the seemingly impossible, initially explained by some reviewers as either sleight of hand or the misinterpretation by an overzealous young scientist of results reported many years before and having little utility. The "magic" that we were attempting to report was that with matrix assistance, molecules, at least as large as bovine serum albumin (66 kDa), are lifted into the gas phase as multiply charged ions simply by exposure of the matrix:analyte sample to the vacuum of a mass spectrometer. Applied heat, a laser, or voltages are not necessary to achieve charge states and ion abundances only previously observed with electrospray ionization (ESI). The fundamentals of how solid phase volatile or nonvolatile compounds are converted to gas-phase ions without added energy currently involves speculation providing a great opportunity to rethink mechanistic understanding of ionization processes used in mass spectrometry. Improved understanding of the mechanism(s) of these processes and their connection to ESI and matrix-assisted laser desorption/ionization may provide opportunities to further develop new ionization strategies for traditional and yet unforeseen applications of mass spectrometry. This Critical Insights article covers developments leading to the discovery of a seemingly magic ionization process that is simple to use, fast, sensitive, robust, and can be directly applied to surface characterization using portable or high performance mass spectrometers.

  14. "Magic" Ionization Mass Spectrometry.

    PubMed

    Trimpin, Sarah

    2016-01-01

    The systematic study of the temperature and pressure dependence of matrix-assisted ionization (MAI) led us to the discovery of the seemingly impossible, initially explained by some reviewers as either sleight of hand or the misinterpretation by an overzealous young scientist of results reported many years before and having little utility. The “magic” that we were attempting to report was that with matrix assistance, molecules, at least as large as bovine serum albumin (66 kDa), are lifted into the gas phase as multiply charged ions simply by exposure of the matrix:analyte sample to the vacuum of a mass spectrometer. Applied heat, a laser, or voltages are not necessary to achieve charge states and ion abundances only previously observed with electrospray ionization (ESI). The fundamentals of how solid phase volatile or nonvolatile compounds are converted to gas-phase ions without added energy currently involves speculation providing a great opportunity to rethink mechanistic understanding of ionization processes used in mass spectrometry. Improved understanding of the mechanism(s) of these processes and their connection to ESI and matrix-assisted laser desorption/ionization may provide opportunities to further develop new ionization strategies for traditional and yet unforeseen applications of mass spectrometry. This Critical Insights article covers developments leading to the discovery of a seemingly magic ionization process that is simple to use, fast, sensitive, robust, and can be directly applied to surface characterization using portable or high performance mass spectrometers.

  15. Marshall N. Rosenbluth Outstanding Doctoral Thesis Award Talk: The Ultrafast Nonlinear Response of Air Molecules and its Effect on Femtosecond Laser Plasma Filaments in Atmosphere

    NASA Astrophysics Data System (ADS)

    Chen, Yu-Hsin

    2012-10-01

    When exceeding the critical power Pcr, an intense laser pulse propagating in a gas collapses into one or multiple ``filaments,'' which can extend meters in length with weakly ionized plasma and local intensity ˜ 10^13 W/cm^2 radially confined in a diameter of < 100 μm [1]. While it has been generally accepted the nonlinear self-focusing of the laser pulse leading to beam collapse is stabilized by plasma generation [2], neither the field-induced nonlinearity nor the plasma generation had been directly measured. This uncertainty has given rise to recent controversy about whether plasma generation does indeed counteract the positive nonlinearity [3, 4]. For even a basic understanding of femtosecond filamentation and for applications, the focusing and defocusing mechanisms---nonlinear self-focusing and ionization---must be understood. By employing a single-shot, time-resolved technique based on spectral interferometry [5] to study the constituents of air, it is found that the rotational responses in O2 and N2 are the dominant nonlinear effect in filamentary propagation when the laser pulse duration is longer than ˜ 100fs. Furthermore, we find that the instantaneous nonlinearity scales linearly up to the ionization threshold [6], eliminating any possibility of an ionization-free negative stabilization [3] of filamentation. This is confirmed by space-resolved electron density measurements in meter-long filaments produced with different pulse durations, using optical interferometry with a grazing-incidence, ps-delayed probe [7].[4pt] [1] A. Braun et al., Opt. Lett. 20, 73 (1995).[0pt] [2] A. Couairon and A. Mysyrowicz, Phys. Rep. 441, 47 (2007).[0pt] [3] V. Loriot et al., Opt. Express 17, 13429 (2009).[0pt] [4] P. B'ejot et al., Phys. Rev. Lett. 104, 103903 (2010).[0pt] [5] Y.-H. Chen et al., Opt. Express 15, 7458 (2007); Opt. Express 15, 11341 (2007).[0pt] [6] J. K. Wahlstrand et al., Phys. Rev. Lett. 107, 103901 (2011).[0pt] [7] Y.-H. Chen et al., Phys. Rev. Lett

  16. Dynamic, self-assembled aggregates of magnetized, millimeter-sized objects rotating at the liquid-air interface: macroscopic, two-dimensional classical artificial atoms and molecules.

    PubMed

    Grzybowski, B A; Jiang, X; Stone, H A; Whitesides, G M

    2001-07-01

    This paper describes self-assembly of millimeter-sized, magnetized disks floating on a liquid-air interface, and rotating under the influence of a rotating external magnetic field. Spinning of the disks results in hydrodynamic repulsion between them, while the rotating magnetic field produces an average confining potential acting on all disks. The interplay between hydrodynamic and magnetic interactions leads to the formation of patterns. Theoretical analysis of hydrodynamic and magnetic forces indicates that the interactions in this system are similar to those acting in systems of finite numbers of particles behaving classically ("classical artificial atoms"). Macroscopic artificial atoms and molecules are described, and the rules governing their morphologies outlined.

  17. Influence of turn (or fold) and local charge in fragmentation of the peptide analogue molecule CH3CO-Gly-NH2 following single-photon VUV (118.22 nm) ionization.

    PubMed

    Bhattacharya, Atanu; Bernstein, Elliot R

    2011-10-01

    The radical cationic reactivity of the peptide analogue molecule CH(3)CO-Gly-NH(2) is addressed both experimentally and theoretically. The radical cation intermediate of CH(3)CO-Gly-NH(2) is created by single-photon ionization of this molecule at 118.22 nm (~10.5 eV). The two most stable conformers (C(7) and C(5)) of this molecule exhibit different folds along the backbone: the C(7) conformer has a γ-turn structure, and the C(5) conformer has a β-strand structure. The experimental results show that the radical cation intermediate of CH(3)CO-Gly-NH(2) dissociates and generates a fragment-ion signal at 73 amu that is observed through TOFMS. Theoretical results show how the fragment-ion signal at 73 amu is generated by only one conformer of CH(3)CO-Gly-NH(2) (C(7)) and how local charge and specific hydrogen bonding in the molecule influence fragmentation of the radical cation intermediate of CH(3)CO-Gly-NH(2). The specific fold of the molecule controls fragmentation of this reactive radical cation intermediate. Whereas the radical cation of the C(7) conformer dissociates through a hydrogen-transfer mechanism followed by HNCO elimination, the radical cation of the C(5) conformer does not dissociate at all. CASSCF calculations show that positive charge in the radical cationic C(7) conformer is localized at the NH(2)CO moiety of the molecular ion. This site-specific localization of the positive charge enhances the acidity of the terminal NH(2) group, facilitating hydrogen transfer from the NH(2) to the COCH(3) end of the molecular ion. Positive charge in the C(5) conformer of the CH(3)CO-Gly-NH(2) radical cation is, however, localized at the COCH(3) end of the molecular ion, and this conformer does not have enough energy to surmount the energy barrier to dissociation on the ion potential energy surface. CASSCF results show that conformation-specific localization of charge in the CH(3)CO-Gly-NH(2) molecular ion occurs as a result of the different hydrogen

  18. Formation of complex organic molecules in methanol and methanol-carbon monoxide ices exposed to ionizing radiation--a combined FTIR and reflectron time-of-flight mass spectrometry study.

    PubMed

    Maity, Surajit; Kaiser, Ralf I; Jones, Brant M

    2015-02-01

    The radiation induced chemical processing of methanol and methanol-carbon monoxide ices at 5.5 K exposed to ionizing radiation in the form of energetic electrons and subsequent temperature programmed desorption is reported in this study. The endogenous formation of complex organic molecules was monitored online and in situ via infrared spectroscopy in the solid state and post irradiation with temperature programmed desorption (TPD) using highly sensitive reflectron time-of-flight (ReTOF) mass spectrometry coupled with single photoionization at 10.49 eV. Infrared spectroscopic analysis of the processed ice systems resulted in the identification of simple molecules including the hydroxymethyl radical (CH2OH), formyl radical (HCO), methane (CH4), formaldehyde (H2CO), carbon dioxide (CO2), ethylene glycol (HOCH2CH2OH), glycolaldehyde (HOCH2CHO), methyl formate (HCOOCH3), and ketene (H2CCO). In addition, ReTOF mass spectrometry of subliming molecules following temperature programmed desorption definitely identified several closed shell C/H/O bearing organics including ketene (H2CCO), acetaldehyde (CH3COH), ethanol (C2H5OH), dimethyl ether (CH3OCH3), glyoxal (HCOCOH), glycolaldehyde (HOCH2CHO), ethene-1,2-diol (HOCHCHOH), ethylene glycol (HOCH2CH2OH), methoxy methanol (CH3OCH2OH) and glycerol (CH2OHCHOHCH2OH) in the processed ice systems. Additionally, an abundant amount of molecules yet to be specifically identified were observed sublimating from the irradiated ices including isomers with the formula C3H(x=4,6,8)O, C4H(x=8,10)O, C3H(x=4,6,8)O2, C4H(x=6,8)O2, C3H(x=4,6)O3, C4H8O3, C4H(x=4,6,8)O4, C5H(x=6,8)O4 and C5H(x=6,8)O5. The last group of molecules containing four to five oxygen atoms observed sublimating from the processed ice samples include an astrobiologically important class of sugars relevant to RNA, phospholipids and energy storage. Experiments are currently being designed to elucidate their chemical structure. In addition, several reaction pathways were

  19. Electrospray Ionization Mass Spectrometry

    SciTech Connect

    Kelly, Ryan T.; Marginean, Ioan; Tang, Keqi

    2014-06-13

    Electrospray Ionization (ESI) is a process whereby gas phase ions are created from molecules in solution. As a solution exits a narrow tube in the presence of a strong electric field, an aerosol of charged droplets are is formed that produces gas phase ions as they it desolvates. ESI-MS comprises the creation of ions by ESI and the determination of their mass to charge ratio (m/z) by MS.

  20. INDUSTRIAL EFFLUENT TREATMENT USING IONIZING RADIATION COMBINED TO TITANIUM DIOXIDE

    SciTech Connect

    Duarte, C.L.; Oikawa, H.; Mori, M.N.; Sampa, M.H.O.

    2004-10-04

    The Advanced Oxidation Process (AOP) with OH radicals are the most efficient to mineralize organic compounds, and there are various methods to generate OH radicals as the use of ozone, hydrogen peroxide and ultra-violet radiation and ionizing radiation. The irradiation of aqueous solutions with high-energy electrons results in the excitation and ionizing of the molecules and rapid (10{sup -14} - 10{sup -9} s) formation of reactive intermediates. These reactive species will react with organic compounds present in industrial effluent inducing their decomposition. Titanium dioxide (TiO{sub 2}) catalyzed photoreaction is used to remove a wide range of pollutants in air and water media, combined to UV/VIS light, FeO{sub 2}, and H{sub 2}O{sub 2}, but as far as known there is no report on the combination with ionizing radiation. In some recent studies, the removal of organic pollutants in industrial effluent, such as Benzene, Toluene, and Xylene from petroleum production using ionizing radiation was investigated. It has been ob served that none of the methods can be used individually in wastewater treatment applications with good economics and high degree of energy efficiency. In the present work, the efficiency of ionizing radiation in presence of TiO{sub 2} to treat industrial effluent was evaluated. The main aim to combine these technologies is to improve the efficiency for very hard effluents and to reduce the processing cost for future implementation to large-scale design.

  1. Collisional energy transfer probabilities of highly excited molecules from kinetically controlled selective ionization (KCSI). II. The collisional relaxation of toluene: P(E',E) and moments of energy transfer for energies up to 50 000 cm-1

    NASA Astrophysics Data System (ADS)

    Lenzer, Thomas; Luther, Klaus; Reihs, Karsten; Symonds, Andrew C.

    2000-03-01

    Complete and detailed experimental transition probability density functions P(E',E) have been determined for the first time for collisions between a large, highly vibrationally excited molecule, toluene, and several bath gases. This was achieved by applying the method of kinetically controlled selective ionization (KCSI) (Paper I [J. Chem. Phys. 112, 4076 (2000), preceding article]). An optimum P(E',E) representation is recommended (monoexponential with a parametric exponent in the argument) which uses only three parameters and features a smooth behavior of all parameters for the entire set of bath gases. In helium, argon, and CO2 the P(E',E) show relatively increased amplitudes in the wings—large energy gaps |E'-E|—which can also be represented by a biexponential form. The fractional contribution of the second exponent in these biexponentials, which is directly related to the fraction of the so-called "supercollisions," is found to be very small (<0.1%). For larger colliders the second term disappears completely and the wings of P(E',E) have an even smaller amplitude than that provided by a monoexponential form. At such low levels, the second exponent is therefore of practically no relevance for the overall energy relaxation rate. All optimized P(E',E) representations show a marked linear energetic dependence of the (weak) collision parameter α1(E), which also results in an (approximately) linear dependence of <ΔE> and of the square root of <ΔE2>. The energy transfer parameters presented in this study form a new benchmark class in certainty and accuracy, e.g., with only 2%-7% uncertainty for our <ΔE> data below 25 000 cm-1. They should also form a reliable testground for future trajectory calculations and theories describing collisional energy transfer of polyatomic molecules.

  2. Photo-double ionization of molecular hydrogen

    NASA Astrophysics Data System (ADS)

    Walter, Michael; Briggs, John

    1999-06-01

    The angular distribution of the correlated electron pair emitted in single-photon double ionization of the hydrogen molecule is analysed and calculated using a variety of approximations. Attention is directed particularly towards the differences between the molecular angular distribution and that of the corresponding `united atom', i.e. that arising from the double ionization of helium. Qualitative agreement is obtained with recent experiments on photo-double ionization of the hydrogen molecule. The major effects arising from the two-centre nuclear field of the molecule and the orientation of the axis at the moment of photon absorption are exposed in the simpler problem of photoionization of the H2+ ion.

  3. Practical method for determination of air kerma by use of an ionization chamber toward construction of a secondary X-ray field to be used in clinical examination rooms.

    PubMed

    Maehata, Itsumi; Hayashi, Hiroaki; Kimoto, Natsumi; Takegami, Kazuki; Okino, Hiroki; Kanazawa, Yuki; Tominaga, Masahide

    2016-07-01

    We propose a new practical method for the construction of an accurate secondary X-ray field using medical diagnostic X-ray equipment. For accurate measurement of the air kerma of an X-ray field, it is important to reduce and evaluate the contamination rate of scattered X-rays. To determine the rate quantitatively, we performed the following studies. First, we developed a shield box in which an ionization chamber could be set at an inner of the box to prevent detection of the X-rays scattered from the air. In addition, we made collimator plates which were placed near the X-ray source for estimation of the contamination rate by scattered X-rays from the movable diaphragm which is a component of the X-ray equipment. Then, we measured the exposure dose while changing the collimator plates, which had diameters of 25-90 mm(ϕ). The ideal value of the exposure dose was derived mathematically by extrapolation to 0 mm(ϕ). Tube voltages ranged from 40 to 130 kV. Under these irradiation conditions, we analyzed the contamination rate by the scattered X-rays. We found that the contamination rates were less than 1.7 and 2.3 %, caused by air and the movable diaphragm, respectively. The extrapolated value of the exposure dose has been determined to have an uncertainty of 0.7 %. The ionization chamber used in this study was calibrated with an accuracy of 5 %. Using this kind of ionization chamber, we can construct a secondary X-ray field with an uncertainty of 5 %.

  4. Efficient Ionization Investigation for Flow Control and Energy Extraction

    NASA Technical Reports Server (NTRS)

    Schneider, Steven J.; Kamhawi, Hani; Blankson, Isaiah M.

    2009-01-01

    Nonequilibrium ionization of air by nonthermal means is explored for hypersonic vehicle applications. The method selected for evaluation generates a weakly ionized plasma using pulsed nanosecond, high-voltage discharges sustained by a lower dc voltage. These discharges promise to provide a means of energizing and sustaining electrons in the air while maintaining a nearly constant ion/neutral molecule temperature. This paper explores the use of short approx.5 nsec, high-voltage approx.12 to 22 kV, repetitive (40 to 100 kHz) discharges in generating a weakly ionized gas sustained by a 1 kV dc voltage in dry air at pressures from 10 to 80 torr. Demonstrated lifetimes of the sustainer discharge current approx.10 to 25 msec are over three orders of magnitude longer than the 5 nsec pulse that generates the electrons. This life is adequate for many high speed flows, enabling the possibility of exploiting weakly ionized plasma phenomena in flow-fields such as those in hypersonic inlets, combustors, and nozzles. Results to date are obtained in a volume of plasma between electrodes in a bell jar. The buildup and decay of the visible emission from the pulser excited air is photographed on an ICCD camera with nanosecond resolution and the time constants for visible emission decay are observed to be between 10 to 15 nsec decreasing as pressure increases. The application of the sustainer voltage does not change the visible emission decay time constant. Energy consumption as indicated by power output from the power supplies is 194 to 669 W depending on pulse repetition rate.

  5. Effect of perfluoroalkyl chain length on monolayer behavior of partially fluorinated oleic acid molecules at the air-water interface.

    PubMed

    Baba, Teruhiko; Takai, Katsuki; Takagi, Toshiyuki; Kanamori, Toshiyuki

    2013-01-01

    A series of oleic acid (OA) analogs containing terminal perfluoroalkyl groups (CF3, C2F5, n-C3F7, n-C4F9 or n-C8F17) was synthesized to clarify how the fluorinated chain length affects the stability and molecular packing of liquid-expanded OA monolayers at the air-water interface. Although the substitution of terminal CF3 group for CH3 in OA had no effect on monolayer stability, further fluorination led to a gradual increase in monolayer stability at 25 °C. Surface pressure-area isotherm revealed that partially fluorinated OA analogs form more expanded monolayers than OA at low surface pressures, and that the monolayer behavior of OA analogs with the even-carbon numbered fluorinated chain is almost the same as that of OA upon monolayer compression, whereas the behavior of OA analogs with the odd-carbon numbered fluorinated chain significantly differs from that of OA. These results indicate: (i) the terminal short part (at least C2 residue) in OA predominantly determines the liquid-expanded monolayer stability; (ii) the molecular packing state of OA may be perturbed by the substitution of a short odd-carbon numbered fluorinated chain; (iii) hence, OA analogs with even-carbon numbered chain are considered to be preferable as hydrophobic building blocks for the synthesis of fluorinated phospholipids.

  6. Ionization chamber

    DOEpatents

    Walenta, Albert H.

    1981-01-01

    An ionization chamber has separate drift and detection regions electrically isolated from each other by a fine wire grid. A relatively weak electric field can be maintained in the drift region when the grid and another electrode in the chamber are connected to a high voltage source. A much stronger electric field can be provided in the detection region by connecting wire electrodes therein to another high voltage source. The detection region can thus be operated in a proportional mode when a suitable gas is contained in the chamber. High resolution output pulse waveforms are provided across a resistor connected to the detection region anode, after ionizing radiation enters the drift region and ionize the gas.

  7. Ionization chamber

    DOEpatents

    Walenta, A.H.

    An ionization chamber is described which has separate drift and detection regions electrically isolated from each other by a fine wire grid. A relatively weak electric field can be maintained in the drift region when the grid and another electrode in the chamber are connected to a high voltage source. A much stronger electric field can be provided in the detection region by connecting wire electrodes therein to another high voltage source. The detection region can thus be operated in a proportional mode when a suitable gas is contained in the chamber. High resolution output pulse waveforms are provided across a resistor connected to the detection region anode, after ionizing radiation enters the drift region and ionizes the gas.

  8. IONIZATION CHAMBER

    DOEpatents

    Redman, W.C.; Shonka, F.R.

    1958-02-18

    This patent describes a novel ionization chamber which is well suited to measuring the radioactivity of the various portions of a wire as the wire is moved at a uniform speed, in order to produce the neutron flux traverse pattern of a reactor in which the wire was previously exposed to neutron radiation. The ionization chamber of the present invention is characterized by the construction wherein the wire is passed through a tubular, straight electrode and radiation shielding material is disposed along the wire except at an intermediate, narrow area where the second electrode of the chamber is located.

  9. The method for on-site determination of trace concentrations of methyl mercaptan and dimethyl sulfide in air using a mobile mass spectrometer with atmospheric pressure chemical ionization, combined with a fast enrichment/separation system.

    PubMed

    Kudryavtsev, Andrey S; Makas, Alexey L; Troshkov, Mikhail L; Grachev, Mikhail А; Pod'yachev, Sergey P

    2014-06-01

    A method for fast simultaneous on-site determination of methyl mercaptan and dimethyl sulfide in air was developed. The target compounds were actively collected on silica gel, followed by direct flash thermal desorption, fast separation on a short chromatographic column and detection by means of mass spectrometer with atmospheric pressure chemical ionization. During the sampling of ambient air, water vapor was removed with a Nafion selective membrane. A compact mass spectrometer prototype, which was designed earlier at Trofimuk Institute of Petroleum Geology and Geophysics, was used. The minimization of gas load of the atmospheric pressure ion source allowed reducing the power requirements and size of the vacuum system and increasing its ruggedness. The measurement cycle is about 3 min. Detection limits in a 0.6 L sample are 1 ppb for methyl mercaptan and 0.2 ppb for dimethyl sulfide.

  10. Comparison of sodium naphthenate and air-ionization corona discharge as surface treatments for the ethylene-tetrafluoroethylene polymer (ETFE) to improve adhesion between ETFE and acrylonitrile-butadiene-styrene polymer (ABS) in the presence of a cyanoacrylate adhesive (CAA)

    NASA Astrophysics Data System (ADS)

    Lucía Johanning-Solís, Ana; Stradi-Granados, Benito A.

    2014-09-01

    This study compares two ethylene-tetrafluoroethylene (ETFE) surface activation treatments, namely chemical attack with a solution of sodium naphthenate and plasma erosion via air-ionization corona discharge in order to improve the adhesive properties of the ETFE. An experimental design was prepared for both treatments in order to assess the effect of the treatment characteristics on the tensile load needed to break the bond between the ETFE and the acrylonitrile-butadiene-styrene polymer (ABS) formed with a cyanoacrylate adhesive (CAA) applied between them. The reason for the selection of this problem is that both polymers are frequently used in the biomedical industry for their properties, and they need to be joined firmly in biomedical devices, and the cyanoacrylate adhesive is the adhesive traditionally used for fluoropolymers, in this case the ETFE, and the same CAA has also shown good adhesion with ABS. However, the strength of the bond for the triplet ETFE-CAA-ABS has not been reported and the improvement of the strength of the bond with surface treatments is not found in scholarly journals for modern medical devices such as stents and snares. Both treatments were compared based on the aforementioned design of experiments. The case where ETFE receives no surface treatment serves as the reference. The results indicated that the three factors evaluated (initial drying of the material, temperature of the chemical bath, and immersion time), and their interactions have no significant effect over the tensile load at failure (tensile strength) of the adhesive bond being evaluated. For the air-ionization corona discharge treatment, two factors were evaluated: discharge exposition time and air pressure. The results obtained from this experimental design indicate that there is no significant difference between the levels of the factors evaluated. These results were unexpected as the ranges used were representative of the maximum ranges permissible in manufacturing

  11. Organic heterocyclic molecules become superalkalis.

    PubMed

    Reddy, G Naaresh; Giri, Santanab

    2016-09-21

    An organic molecule which behaves like a superalkali has been designed from an aromatic heterocyclic molecule, pyrrole. Using first-principles calculation and a systematic two-step approach, we can have superalkali molecules with a low ionization energy, even lower than that of Cs. Couple cluster (CCSD) calculation reveals that a new heterocycle, C3N2(CH3)5 derived from a well-known aromatic heterocycle, pyrrole (C4H5N) has an ionization energy close to 3.0 eV. A molecular dynamics calculation on C3N2(CH3)5 reveals that the structure is dynamically stable. PMID:27530344

  12. Experiments of discharge guiding using strongly and weakly ionized plasma channels for laser-triggered lightning

    NASA Astrophysics Data System (ADS)

    Shimada, Yoshinori; Uchida, Shigeaki; Yamanaka, Chiyoe; Ogata, Akihisa; Yamanaka, Tatsuhiko; Kawasaki, Zen-ichiro; Fujiwara, Etsuo; Ishikubo, Yuji; Kawabata, Kinya

    2000-01-01

    Generation of a long laser-plasma channel capable of triggering and guiding an electrical discharge is a crucial issue for laser-triggering protection system. We make a long plasma channel to increase the probability of triggered lightning by laser. To produce a long laser plasma channel, we propose da new technique called hybrid plasma channel method which combines weakly and strongly ionized plasma channels to maximize laser-energy efficiency of discharge guiding. We investigate the characteristics of the hybrid plasma channels to maximize laser-energy efficiency of discharge guiding. We investigate the characteristics of the hybrid plasma channel method through several laboratory experiments. The weakly ionized channel was generated by UV laser pulses in air. As the number density of electrons in weakly ionized channel is proportional to 1.1 power of laser intensity, nitrogen and oxygen molecules can not attributed to the source of ionized plasma. It is suggested that dissociation process of impurities in air whose density is 1011 - 1012 cm-3 plays an important role in plasma formation and leader triggering effect. The 50 percent flashover voltage using the hybrid plasma channel method is lower than that without the weakly ionized plasma channel. It was also found that higher repetition rate of the plasma generation on lowers the V50 furthermore.

  13. NBC detection in air and water

    NASA Technical Reports Server (NTRS)

    Hartley, Frank T.; Smith, Steven J.; McMurtry, Gary M.

    2003-01-01

    Participating in a Navy STTR project to develop a system capable of the 'real-time' detection and quanitification of nuclear, biological and chemical (NBC) warfare agents, and of related industrial chemicals including NBC agent synthesis by-products in water and in air immediately above the water's surface. This project uses JPL's Soft Ionization Membrane (SIM) technology which totally ionizes molecules without fragmentation (a process that can markedly improve the sensitivity and specificity of molecule compostition identification), and JPL's Rotating Field Mass Spectrometer (RFMS) technology which has large enough dynamic mass range to enable detection of nuclear materials as well as biological and chemical agents. This Navy project integrates these JPL Environmental Monitoring UnitS (REMUS) an autonomous underwater vehicle (AUV). It is anticipated that the REMUS AUV will be capable of 'real-time' detection and quantification of NBC warefare agents.

  14. Air heating approach for multilayer etching and roll-to-roll transfer of silicon nanowire arrays as SERS substrates for high sensitivity molecule detection.

    PubMed

    Wang, Yan; Zhang, Xiujuan; Gao, Peng; Shao, Zhibin; Zhang, Xiwei; Han, Yuanyan; Jie, Jiansheng

    2014-01-22

    SiNW array represents an attractive system for construction of high-performance energy, electronic, and sensor devices. To meet the demand for flexible devices as well as address the concern about the full use of the Si material, large-area transfer of the SiNW array from growth substrate is very desirable. Here, we report a simple air heating approach to achieve the multilayer etched SiNW array. This method allows the fabrication of up to a five-layer (while perfectly three-layer) cracked SiNW array on single-crystalline Si wafer via a templateless metal-assisted etching approach. Fractures could happen at the crack position when an appropriate pressure was applied on the SiNW array, facilitating the wafer-scale layer-by-layer transfer of the SiNW array onto a flexible substrate through a low-cost and time-efficient roll-to-roll (R2R) technique. Further releasing of the SiNW array to other receiving substrates was accomplished with the aid of a thermal release tape. After modification with sliver nanoparticles (AgNPs), the flexible SiNW array showed great potential as a high-sensitivity surface-enhanced Raman spectroscopy (SERS) substrate for detecting rhodamine 6G (R6G) molecule with concentration as low as 10(-9) M.

  15. Rovibrationally selected ion-molecule collision study using the molecular beam vacuum ultraviolet laser pulsed field ionization-photoion method: Charge transfer reaction of N2+(X 2Σg+; v+ = 0-2; N+ = 0-9) + Ar

    NASA Astrophysics Data System (ADS)

    Chang, Yih Chung; Xu, Yuntao; Lu, Zhou; Xu, Hong; Ng, C. Y.

    2012-09-01

    We have developed an ion-molecule reaction apparatus for state-selected absolute total cross section measurements by implementing a high-resolution molecular beam vacuum ultraviolet (VUV) laser pulsed field ionization-photoion (PFI-PI) ion source to a double-quadrupole double-octopole ion-guide mass spectrometer. Using the total cross section measurement of the state-selected N2+(v+, N+) + Ar charge transfer (CT) reaction as an example, we describe in detail the design of the VUV laser PFI-PI ion source used, which has made possible the preparation of reactant N2+(X 2Σg+, v+ = 0-2, N+ = 0-9) PFI-PIs with high quantum state purity, high intensity, and high kinetic energy resolution. The PFI-PIs and prompt ions produced in the ion source are shown to have different kinetic energies, allowing the clean rejection of prompt ions from the PFI-PI beam by applying a retarding potential barrier upstream of the PFI-PI source. By optimizing the width and amplitude of the pulsed electric fields employed to the VUV-PFI-PI source, we show that the reactant N2+ PFI-PI beam can be formed with a laboratory kinetic energy resolution of ΔElab = ± 50 meV. As a result, the total cross section measurement can be conducted at center-of-mass kinetic energies (Ecm's) down to thermal energies. Absolute total rovibrationally selected cross sections σ(v+ = 0-2, N+ = 0-9) for the N2+(X 2Σg+; v+ = 0-2, N+ = 0-9) + Ar CT reaction have been measured in the Ecm range of 0.04-10.0 eV, revealing strong vibrational enhancements and Ecm-dependencies of σ(v+ = 0-2, N+ = 0-9). The thermochemical threshold at Ecm = 0.179 eV for the formation of Ar+ from N2+(X; v+ = 0, N+) + Ar was observed by the measured σ(v+ = 0), confirming the narrow ΔEcm spread achieved in the present study. The σ(v+ = 0-2; N+) values obtained here are compared with previous experimental and theoretical results. The theoretical predictions calculated based on the Landau-Zener-Stückelberg formulism are found to be in fair

  16. Multiphoton ionization of ions, neutrals, and clusters. Progress report

    SciTech Connect

    Wessel, J.

    1991-06-28

    Scientific results are summarized from a three year research program on multiphoton ionization in aromatic molecules, clusters, and their ions. As originally proposed, the studies elucidated a new cluster ionization mechanism, characterized properties of long range intermolecular interactions, and investigated electronic transitions of aromatic cations cooled in a supersonic beam. The studies indicate that the new cluster ionization mechanism is highly efficient and dominates conventional 1 + 1 resonant ionization. In the case of the dimer of the large aromatic molecule fluorene, the results suggest that excimer formation competes with a direct ionization process. Highly selective excitonic spectra have been identified for several cluster species.

  17. 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.

  18. In-Line Reactions and Ionizations of Vaporized Diphenylchloroarsine and Diphenylcyanoarsine in Atmospheric Pressure Chemical Ionization Mass Spectrometry.

    PubMed

    Okumura, Akihiko; Takada, Yasuaki; Watanabe, Susumu; Hashimoto, Hiroaki; Ezawa, Naoya; Seto, Yasuo; Takayama, Yasuo; Sekioka, Ryoji; Yamaguchi, Shintaro; Kishi, Shintaro; Satoh, Takafumi; Kondo, Tomohide; Nagashima, Hisayuki; Nagoya, Tomoki

    2016-07-01

    We propose detecting a fragment ion (Ph2As(+)) using counter-flow introduction atmospheric pressure chemical ionization ion trap mass spectrometry for sensitive air monitoring of chemical warfare vomiting agents diphenylchloroarsine (DA) and diphenylcyanoarsine (DC). The liquid sample containing of DA, DC, and bis(diphenylarsine)oxide (BDPAO) was heated in a dry air line, and the generated vapor was mixed into the humidified air flowing through the sampling line of a mass spectrometer. Humidity effect on the air monitoring was investigated by varying the humidity of the analyzed air sample. Evidence of the in-line conversion of DA and DC to diphenylarsine hydroxide (DPAH) and then BDPAO was obtained by comparing the chronograms of various ions from the beginning of heating. Multiple-stage mass spectrometry revealed that the protonated molecule (MH(+)) of DA, DC, DPAH, and BDPAO could produce Ph2As(+) through their in-source fragmentation. Among the signals of the ions that were investigated, the Ph2As(+) signal was the most intense and increased to reach a plateau with the increased air humidity, whereas the MH(+) signal of DA decreased. It was suggested that DA and DC were converted in-line into BDPAO, which was a major source of Ph2As(+). Graphical Abstract ᅟ.

  19. In-Line Reactions and Ionizations of Vaporized Diphenylchloroarsine and Diphenylcyanoarsine in Atmospheric Pressure Chemical Ionization Mass Spectrometry.

    PubMed

    Okumura, Akihiko; Takada, Yasuaki; Watanabe, Susumu; Hashimoto, Hiroaki; Ezawa, Naoya; Seto, Yasuo; Takayama, Yasuo; Sekioka, Ryoji; Yamaguchi, Shintaro; Kishi, Shintaro; Satoh, Takafumi; Kondo, Tomohide; Nagashima, Hisayuki; Nagoya, Tomoki

    2016-07-01

    We propose detecting a fragment ion (Ph2As(+)) using counter-flow introduction atmospheric pressure chemical ionization ion trap mass spectrometry for sensitive air monitoring of chemical warfare vomiting agents diphenylchloroarsine (DA) and diphenylcyanoarsine (DC). The liquid sample containing of DA, DC, and bis(diphenylarsine)oxide (BDPAO) was heated in a dry air line, and the generated vapor was mixed into the humidified air flowing through the sampling line of a mass spectrometer. Humidity effect on the air monitoring was investigated by varying the humidity of the analyzed air sample. Evidence of the in-line conversion of DA and DC to diphenylarsine hydroxide (DPAH) and then BDPAO was obtained by comparing the chronograms of various ions from the beginning of heating. Multiple-stage mass spectrometry revealed that the protonated molecule (MH(+)) of DA, DC, DPAH, and BDPAO could produce Ph2As(+) through their in-source fragmentation. Among the signals of the ions that were investigated, the Ph2As(+) signal was the most intense and increased to reach a plateau with the increased air humidity, whereas the MH(+) signal of DA decreased. It was suggested that DA and DC were converted in-line into BDPAO, which was a major source of Ph2As(+). Graphical Abstract ᅟ. PMID:27098411

  20. In-Line Reactions and Ionizations of Vaporized Diphenylchloroarsine and Diphenylcyanoarsine in Atmospheric Pressure Chemical Ionization Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Okumura, Akihiko; Takada, Yasuaki; Watanabe, Susumu; Hashimoto, Hiroaki; Ezawa, Naoya; Seto, Yasuo; Takayama, Yasuo; Sekioka, Ryoji; Yamaguchi, Shintaro; Kishi, Shintaro; Satoh, Takafumi; Kondo, Tomohide; Nagashima, Hisayuki; Nagoya, Tomoki

    2016-07-01

    We propose detecting a fragment ion (Ph2As+) using counter-flow introduction atmospheric pressure chemical ionization ion trap mass spectrometry for sensitive air monitoring of chemical warfare vomiting agents diphenylchloroarsine (DA) and diphenylcyanoarsine (DC). The liquid sample containing of DA, DC, and bis(diphenylarsine)oxide (BDPAO) was heated in a dry air line, and the generated vapor was mixed into the humidified air flowing through the sampling line of a mass spectrometer. Humidity effect on the air monitoring was investigated by varying the humidity of the analyzed air sample. Evidence of the in-line conversion of DA and DC to diphenylarsine hydroxide (DPAH) and then BDPAO was obtained by comparing the chronograms of various ions from the beginning of heating. Multiple-stage mass spectrometry revealed that the protonated molecule (MH+) of DA, DC, DPAH, and BDPAO could produce Ph2As+ through their in-source fragmentation. Among the signals of the ions that were investigated, the Ph2As+ signal was the most intense and increased to reach a plateau with the increased air humidity, whereas the MH+ signal of DA decreased. It was suggested that DA and DC were converted in-line into BDPAO, which was a major source of Ph2As+.

  1. Fluid hydrogen at high density - Pressure ionization

    NASA Technical Reports Server (NTRS)

    Saumon, Didier; Chabrier, Gilles

    1992-01-01

    The Helmholtz-free-energy model for nonideal mixtures of hydrogen atoms and molecules by Saumon and Chabrier (1991) is extended to describe dissociation and ionization in similar mixtures in chemical equilibrium. A free-energy model is given that describes partial ionization in the pressure and temperature ionization region. The plasma-phase transition predicted by the model is described for hydrogen mixtures including such components as H2, H, H(+), and e(-). The plasma-phase transition has a critical point at Tc = 15,300 K and Pc = 0.614 Mbar, and thermodynamic instability is noted in the pressure-ionization regime. The pressure dissociation and ionization of fluid hydrogen are described well with the model yielding information on the nature of the plasma-phase transition. The model is shown to be valuable for studying dissociation and ionization in astrophysical objects and in high-pressure studies where pressure and temperature effects are significant.

  2. Atmospheric sampling glow discharge ionization source

    DOEpatents

    McLuckey, S.A.; Glish, G.L.

    1989-07-18

    An atmospheric sampling glow discharge ionization source that can be used in combination with an analytical instrument which operates at high vacuum, such as a mass spectrometer. The atmospheric sampling glow discharge ionization source comprises a chamber with at least one pair of electrodes disposed therein, an inlet for a gaseous sample to be analyzed and an outlet communicating with an analyzer which operates at subatmospheric pressure. The ionization chamber is maintained at a pressure below atmospheric pressure, and a voltage difference is applied across the electrodes to induce a glow discharge between the electrodes, so that molecules passing through the inlet are ionized by the glow discharge and directed into the analyzer. The ionization source accepts the sample under atmospheric pressure conditions and processes it directly into the high vacuum instrument, bridging the pressure gap and drawing off unwanted atmospheric gases. The invention also includes a method for analyzing a gaseous sample using the glow discharge ionization source described above. 3 figs.

  3. Atmospheric sampling glow discharge ionization source

    DOEpatents

    McLuckey, Scott A.; Glish, Gary L.

    1989-01-01

    An atmospheric sampling glow discharge ionization source that can be used in combination with an analytical instrument which operates at high vacuum, such as a mass spectrometer. The atmospheric sampling glow discharge ionization source comprises a chamber with at least one pair of electrodes disposed therein, an inlet for a gaseous sample to be analyzed and an outlet communicating with an analyzer which operates at subatmospheric pressure. The ionization chamber is maintained at a pressure below atmospheric pressure, and a voltage difference is applied across the electrodes to induce a glow discharge between the electrodes, so that molecules passing through the inlet are ionized by the glow discharge and directed into the analyzer. The ionization source accepts the sample under atmospheric pressure conditions and processes it directly into the high vacuum instrument, bridging the pressure gap and drawing off unwanted atmospheric gases. The invention also includes a method for analyzing a gaseous sample using the glow discharge ionization source described above.

  4. High-efficiency electron ionizer for a mass spectrometer array

    NASA Technical Reports Server (NTRS)

    Chutjian, Ara (Inventor); Darrach, Murray R. (Inventor); Orient, Otto J. (Inventor)

    2001-01-01

    The present invention provides an improved electron ionizer for use in a quadrupole mass spectrometer. The improved electron ionizer includes a repeller plate that ejects sample atoms or molecules, an ionizer chamber, a cathode that emits an electron beam into the ionizer chamber, an exit opening for excess electrons to escape, at least one shim plate to collimate said electron beam, extraction apertures, and a plurality of lens elements for focusing the extracted ions onto entrance apertures.

  5. Method and apparatus to monitor a beam of ionizing radiation

    DOEpatents

    Blackburn, Brandon W.; Chichester, David L.; Watson, Scott M.; Johnson, James T.; Kinlaw, Mathew T.

    2015-06-02

    Methods and apparatus to capture images of fluorescence generated by ionizing radiation and determine a position of a beam of ionizing radiation generating the fluorescence from the captured images. In one embodiment, the fluorescence is the result of ionization and recombination of nitrogen in air.

  6. The FiR 1 photon beam model adjustment according to in-air spectrum measurements with the Mg(Ar) ionization chamber.

    PubMed

    Koivunoro, H; Schmitz, T; Hippeläinen, E; Liu, Y-H; Serén, T; Kotiluoto, P; Auterinen, I; Savolainen, S

    2014-06-01

    The mixed neutron-photon beam of FiR 1 reactor is used for boron-neutron capture therapy (BNCT) in Finland. A beam model has been defined for patient treatment planning and dosimetric calculations. The neutron beam model has been validated with an activation foil measurements. The photon beam model has not been thoroughly validated against measurements, due to the fact that the beam photon dose rate is low, at most only 2% of the total weighted patient dose at FiR 1. However, improvement of the photon dose detection accuracy is worthwhile, since the beam photon dose is of concern in the beam dosimetry. In this study, we have performed ionization chamber measurements with multiple build-up caps of different thickness to adjust the calculated photon spectrum of a FiR 1 beam model.

  7. Theoretical and observational determinations of the ionization coefficient of meteors

    NASA Astrophysics Data System (ADS)

    Jones, William

    1997-07-01

    We examine the problem of the determination of the ionization coefficient beta from both the theoretical and observational points of view. In the past, theoretical evaluations of beta in terms of the relevant scattering cross-sections have used the Massey-Sida formula, which we show to give results which are plainly incorrect. We derive an integral equation for beta and compare the results of its application to copper and iron with laboratory simulations. Agreement for the variation of the ionization coefficient with velocity is good. The ionization coefficient has been determined observationally by Verniani & Hawkins from a comparison of radar and visual observations, employing the luminous efficiency tau also obtained observationally by Verniani. However, this determination of tau would appear to be invalidated by fragmentation. There is good evidence that the radiation of cometary meteors is dominated by that of iron in the visual range, and we have accordingly re-analysed the data of Verniani & Hawkins using the luminous efficiency of iron obtained in simulation experiments. However, it is not possible to choose an iron concentration which gives agreement between the determination of the ionization coefficient by this means and its determination from the theoretical equation in terms of either scattering coefficients or simulation methods. The observational ionization coefficients are much lower than predicted by the present theory and we provisionally explain this as a consequence of transfer of charge from the meteoric ion to a molecule of the air. It is now possible for the meteoric atom to be re-ionized, but it is also possible at sufficiently high initial line densities for significant dissociative recombination of the electrons and nitrogen or oxygen to take place. This recombination will not take place in meteor trains simulated in an ionization chamber. We thus conclude that the present theory is limited to faint radio meteors at lower velocities (v<~35

  8. Effect of Air Ions on Submicron T1 Bacteriophage Aerosols

    PubMed Central

    Happ, John W.; Harstad, J. Bruce; Buchanan, Lee M.

    1966-01-01

    The effect of a high concentration of ionized air molecules on sampling T1 phage aerosols of submicron particle size was evaluated by comparing the phage recoveries of all-glass impingers (AGI-4) and type 6 filter papers. Sampler recoveries of all ionized aerosols were less than the recoveries of nonionized control aerosols. These reductions in recovery were greater with positive ions than with negative ions or ions of mixed polarity. The AGI-4 allowed considerable slippage, which was not affected by the air ions. Type 6 filter paper recoveries were less than AGI-4 recoveries. The air ions did not appear to affect the aerosol particle size as determined by an electron microscope. Images Fig. 1 Fig. 3 PMID:16349691

  9. Miniature Oxidizer Ionizer for a Fuel Cell

    NASA Technical Reports Server (NTRS)

    Hartley, Frank

    2006-01-01

    A proposed miniature device for ionizing the oxygen (or other oxidizing gas) in a fuel cell would consist mostly of a membrane ionizer using the same principles as those of the device described in the earlier article, Miniature Bipolar Electrostatic Ion Thruster (NPO-21057). The oxidizing gas would be completely ionized upon passage through the holes in the membrane ionizer. The resulting positively charged atoms or molecules of oxidizing gas could then, under the influence of the fringe fields of the ionizer, move toward the fuel-cell cathode that would be part of a membrane/electrode assembly comprising the cathode, a solid-electrolyte membrane, and an anode. The electro-oxidized state of the oxidizer atoms and molecules would enhance transfer of them through the cathode, thereby reducing the partial pressure of the oxidizer gas between the ionizer and the fuel-cell cathode, thereby, in turn, causing further inflow of oxidizer gas through the holes in the membrane ionizer. Optionally the ionizer could be maintained at a positive electric potential with respect to the cathode, in which case the resulting electric field would accelerate the ions toward the cathode.

  10. Dissociative ionization of biomolecules

    NASA Astrophysics Data System (ADS)

    Huo, Winifred

    2004-09-01

    Dissociative ionization (DI) by electron impact plays a role in many different applications, including low-temperature plasma processing, the study of space and astrophysical plasmas, and the study of biological damages by high-energy radiation. In the present study, our goal is to understand the health hazard to humans from exposure to radiation during an extended space flight. DI by secondary electrons can damage the DNA, either directly by causing a DNA lesion, or indirectly by producing radicals and cations that attack the DNA. The theoretical model employed makes use of the fact that electronic motion is much faster than nuclear motion, allowing DI to be treated as a two-step process. The first step is electron-impact ionization resulting in a dissociative state of the molecular ion with the same geometry as the neutral molecule. In the second step the ion relaxes from the initial geometry and undergoes unimolecular dissociation. Thus the DI cross section is given by the product of the ionization cross section and the dissociation probability. For the ionization process we use the improved binary-encounter dipole (iBED) model. For unimolecular dissociation, we use the multiconfigurational self-consistent field (MCSCF) method to determine the minimum energy pathways to possible product channels. This model has been applied to study the DI of H_2O, NH_3, and CH_4, and the results are in good agreement with experiment. The DI from the low-lying channels of benzene has also been studied and the dissociation products are compared with photoionization measurements. The DI of the DNA bases guanine and cytosine are then discussed. Of the four DNA bases, guanine has the largest ionization cross section and cytosine has the smallest. The guanine radical cation is considered to be one of the precursors to the primary, direct-type lesions formed in DNA when it is irradiated. Comparison of DI products of guanine and cytosine will be made to understand the differences in

  11. An improved high performance liquid chromatography-photodiode array detection-atmospheric pressure chemical ionization-mass spectrometry method for determination of chlorophylls and their derivatives in freeze-dried and hot-air-dried Rhinacanthus nasutus (L.) Kurz.

    PubMed

    Kao, Tsai Hua; Chen, Chia Ju; Chen, Bing Huei

    2011-10-30

    Rhinacanthus nasutus (L.) Kurz, a traditional Chinese herb possessing antioxidant and anti-cancer activities, has been reported to contain functional components like carotenoids and chlorophylls. However, the variety and amount of chlorophylls remain uncertain. The objectives of this study were to develop a high performance liquid chromatography-photodiode array detection-atmospheric pressure chemical ionization-mass spectrometry (HPLC-DAD-APCI-MS) method for determination of chlorophylls and their derivatives in hot-air-dried and freeze-dried R. nasutus. An Agilent Eclipse XDB-C18 column and a gradient mobile phase composed of methanol/N,N-dimethylformamide (97:3, v/v), acetonitrile and acetone were employed to separate internal standard zinc-phthalocyanine plus 12 cholorophylls and their derivatives within 21 min, including chlorophyll a, chlorophyll a', hydroxychlorophyll a, 15-OH-lactone chlorophyll a, chlorophyll b, chlorophyll b', hydroxychlorophyll b, pheophytin a, pheophytin a', hydroxypheophytin a, hydroxypheophytin a' and pheophytin b in hot-air-dried R. nasutus with flow rate at 1 mL/min and detection at 660 nm. But, in freeze-dried R. nasutus, only 4 chlorophylls and their derivatives, including chlorophyll a, chlorophyll a', chlorophyll b and pheophytin a were detected. Zinc-phthalocyanine was found to be an appropriate internal standard to quantify all the chlorophyll compounds. After quantification by HPLC-DAD, both chlorophyll a and pheophytin a were the most abundant in hot-air-dried R. nasutus, while in freeze-dried R. nasutus, chlorophyll a and chlorophyll b dominated. PMID:22063550

  12. Multiphoton ionization of Uracil

    NASA Astrophysics Data System (ADS)

    Prieto, Eladio; Martinez, Denhi; Guerrero, Alfonso; Alvarez, Ignacio; Cisneros, Carmen

    2016-05-01

    Multiphoton ionization and dissociation of Uracil using a Reflectron time of flight spectrometer was performed along with radiation from the second harmonic of a Nd:YAG laser. Uracil is one of the four nitrogen bases that belong to RNA. The last years special interest has been concentrated on the study of the effects under UV radiation in nucleic acids1 and also in the role that this molecule could have played in the origin and development of life on our planet.2 The MPI mass spectra show that the presence and intensity of the resulting ions strongly depend on the density power. The identification of the ions in the mass spectra is presented. The results are compared with those obtained in other laboratories under different experimental conditions and some of them show partial agreement.3 The present work was supported by CONACYT-Mexico Grant 165410 and DGAPA UNAM Grant IN101215 and IN102613.

  13. Two-step single-ionization mechanisms

    SciTech Connect

    Boeyen, R. W. van; Doering, J. P.; Watanabe, N.; Cooper, J. W.; Coplan, M. A.; Moore, J. H.

    2006-03-15

    In a recent publication [Phys. Rev. Lett. 92, 233202 (2004)] two different electron impact double ionization (e,3e) mechanisms were identified and the way in which two-electron momentum distributions for atoms and molecules could be obtained by triple coincidence (e,3e) measurements was discussed. The apparatus used detected the two ejected electrons both in and out of the scattering plane at an angle of 45 deg. to the momentum transfer direction in triple coincidence with the scattered electron. Ejected electrons detected out of the scattering plane were shown to be a result of two-step double ionization processes. With the same apparatus we have made double coincidence (e,2e) measurements of electron impact single ionization cross sections for ionization of magnesium 3s (valence) and 2p and 2s (inner) shell electrons at incident energies from 400 to 3000 eV in order to obtain more information about two-step ionization. The experimental results were compared with distorted-wave and plane-wave Born approximations carried out to second order. For the experimental conditions, two-step ionization processes involving one ionizing collision and a second elastic collision with the atomic core are the dominant contribution to the measured cross sections. Calculations are in moderate agreement with the data. The angular distributions of the ionized electrons in these two-step ionizations reflect the initial momentum distributions of the target electrons, a result that is analogous with the earlier (e,3e) measurements.

  14. [Development of a chemical ionization time-of-flight mass spectrometer for continuous measurements of atmospheric hydroxyl radical].

    PubMed

    Dou, Jian; Hua, Lei; Hou, Ke-Yong; Jiang, Lei; Xie, Yuan-Yuan; Zhao, Wu-Duo; Chen, Ping; Wang, Wei-Guo; Di, Tian; Li, Hai-Yang

    2014-05-01

    A home-made chemical ionization time-of-flight mass spectrometer (TOFMS) has been developed for continuous measurements of atmospheric hydroxyl radical. Based on the atmospheric pressure chemical ionization technique, an ionization source with orthogonal dual tube structure was adopted in the instrument, which minimized the interference between the reagent gas ionization and the titration reaction. A 63Ni radioactive source was fixed inside one of the orthogonal tubes to generate reactant ion of NO(-)(3) from HNO3 vapor. Hydroxyl radical was first titrated by excess SO2 to form equivalent concentrations of H2SO4 in the other orthogonal tube, and then reacted with NO(-)(3) ions in the chemical ionization chamber, leading to HSO(-)(4) formation. The concentration of atmospheric hydroxyl radical can be directly calculated by measuring the intensities of the HSOj product ions and the NO(-)(3) reactant ions. The analytical capability of the instrument was demonstrated by measuring hydroxyl radical in laboratory air, and the concentration of the hydroxyl radical in the investigated air was calculated to be 1.6 x 106 molecules*cm ', based on 5 seconds integration. The results have shown that the instrument is competent for in situ continuous measurements of atmospheric trace radical.

  15. Inner-orbital ionization of iodine

    NASA Astrophysics Data System (ADS)

    Gibson, George; Smith, Dale; Tagliamonti, Vincent; Dragan, James

    2016-05-01

    Many coincidence techniques exist to study multiple ionization of molecules by strong laser fields. However, the first ionization step is critical in many experiments, although it is more difficult to obtain information about this initial step. We studied the single electron ionization of I2, as it presents interesting opportunities in that it is heavy and does not expand significantly during the laser pulse. Moreover, there are several distinct low-lying valence orbitals from which the electron may be removed. Most importantly, the kinetic energy release of the I+ + I dissociation channel can be measured and should correspond to well-known valence levels and separated atom limits. As it turns out, we must invoke deep valence orbits, built from the 5s electrons, to explain our data. Ionization from deep orbitals may be possible, as they have a smaller critical internuclear separation for enhanced ionization. We would like to acknowledge support from the NSF under Grant No. PHY-1306845.

  16. Dielectric Barrier Discharge Ionization of Perfluorinated Compounds.

    PubMed

    Schütz, Alexander; Brandt, Sebastian; Liedtke, Sascha; Foest, Daniel; Marggraf, Ulrich; Franzke, Joachim

    2015-11-17

    The soft ionization ability based on plasma-jet protonation of molecules initiated by a dielectric barrier discharge ionization source (DBDI) is certainly an interesting application for analytical chemistry. Since the change of an applied sinusoidal voltage may lead to different discharge modes the applied discharge was powered by a square wave generator in order to get a homogeneous plasma. It is known that besides the protonation [M+H](+) of unpolar as well as some polar molecules the homogeneous DBDI can be used to ionize molecules directly [M](+). Here we prove that the DBDI can be applied to exchange fluorine by oxygen of perfluorinated compounds (PFC). PFC are organofluorine compounds with carbon-fluorine and carbon-carbon bonds only but no carbon-hydrogen bonds. While the position of the introduction into the plasma-jet is essential, PFC can be measured in the negative mass spectrometer (MS) mode.

  17. Real-time analysis of polyaromatic hydrocarbons in flames using atmospheric pressure ionization and tandem mass spectrometry

    SciTech Connect

    Sunner, J.; Gahm, K.H.; Ikonomou, M.; Kebarle, P.

    1988-08-01

    The use of Atmospheric Pressure Ionization followed by tandem mass spectrometry (API/MS/MS) for the analysis of flame gases was demonstrated. The hot flame gases from a methane/air laminar diffusion flame were sampled by rapid turbulent mixing with cold nitrogen gas, in a molar ratio of ca. 1 : 10. After 3 ms the gases underwent an additional dilution by a factor of 20 in synthetic air. The gas mixture was ionized by a corona discharge at atmospheric pressure. Subsequent chemical ionization reactions ionize mainly the polyaromatic hydrocarbons, PAHs. The PAH ions were analyzed in a triple quadrupole mass spectrometer. A sequence of PAH ions started with the perinaphthenyl cation, C/sub 13/H/sub 9//sup +/, and extended up to protonated coronene, C/sub 24/H/sub 13//sup +/, and beyond. That the observed ions were indeed protonated PAH molecules was confirmed by comparing the collision-induced dissociation spectra in the MS/MS mode with those of authentic samples. It is argued that most of the ions originate from PAHs that have substituents attached to the polyaromatic skeleton. The identities of the substituents could, however, not be determined. By rapid turbulent mixing of the flame gases with air, the PAHs were partially oxidized. The high mass region of the API spectrum was then dominated by a sequence of singly oxygenated PAHs.

  18. Fundamentals of ambient metastable-induced chemical ionization mass spectrometry and atmospheric pressure ion mobility spectrometry

    NASA Astrophysics Data System (ADS)

    Harris, Glenn A.

    Molecular ionization is owed much of its development from the early implementation of electron ionization (EI). Although dramatically increasing the library of compounds discovered, an inherent problem with EI was the low abundance of molecular ions detected due to high fragmentation leading to the difficult task of the correct chemical identification after mass spectrometry (MS). These problems stimulated the research into new ionization methods which sought to "soften" the ionization process. In the late 1980s the advancements of ionization techniques was thought to have reached its pinnacle with both electrospray ionization (ESI) and matrix-assisted laser desorption/ionization (MALDI). Both ionization techniques allowed for "soft" ionization of large molecular weight and/or labile compounds for intact characterization by MS. Albeit pervasive, neither ESI nor MALDI can be viewed as "magic bullet" ionization techniques. Both techniques require sample preparation which often included native sample destruction, and operation of these techniques took place in sealed enclosures and often, reduced pressure conditions. New open-air ionization techniques termed "ambient MS" enable direct analysis of samples of various physical states, sizes and shapes. One particular technique named Direct Analysis In Real Time (DART) has been steadily growing as one of the ambient tools of choice to ionize small molecular weight (< 1000 Da) molecules with a wide range of polarities. Although there is a large list of reported applications using DART as an ionization source, there have not been many studies investigating the fundamental properties of DART desorption and ionization mechanisms. The work presented in this thesis is aimed to provide in depth findings on the physicochemical phenomena during open-air DART desorption and ionization MS and current application developments. A review of recent ambient plasma-based desorption/ionization techniques for analytical MS is presented in

  19. Molecule nanoweaver

    DOEpatents

    Gerald, II; Rex E.; Klingler, Robert J.; Rathke, Jerome W.; Diaz, Rocio; Vukovic, Lela

    2009-03-10

    A method, apparatus, and system for constructing uniform macroscopic films with tailored geometric assemblies of molecules on the nanometer scale. The method, apparatus, and system include providing starting molecules of selected character, applying one or more force fields to the molecules to cause them to order and condense with NMR spectra and images being used to monitor progress in creating the desired geometrical assembly and functionality of molecules that comprise the films.

  20. Low-density-solvent-based air-assisted liquid-liquid microextraction followed by gas chromatography with flame ionization detection for the determination of synthetic phenolic antioxidants in milk samples.

    PubMed

    Farajzadeh, Mir Ali; Afshar Mogaddam, Mohammad Reza

    2016-03-01

    A simple and rapid sample pretreatment technique termed low-density-solvent-based air-assisted liquid-liquid microextraction has been developed for the extraction and preconcentration of three synthetic phenolic antioxidants including butylated hydroxyanisole, butylated hydroxytoluene, and tert-butyl hydroquinone from milk samples prior to their analysis by gas chromatography with flame ionization detection. In this method, initially trichloroacetic acid as a proteins precipitation agent is added to the sample, and then it is sonicated and centrifuged. The obtained aqueous phase is removed and the analytes extracted by the proposed method using a low-density organic solvent. Some important parameters such as type and volume of extraction solvent, ionic strength, pH, and centrifugation rate and time were studied. Under the optimum conditions, enrichment factors were obtained in the range of 501-614. LODs and quantification were between 0.76-1.16 and 2.66-3.96 ng mL(-1) , respectively. This method is rapid and requires less than 15 min for sample preparation.

  1. Low-density-solvent-based air-assisted liquid-liquid microextraction followed by gas chromatography with flame ionization detection for the determination of synthetic phenolic antioxidants in milk samples.

    PubMed

    Farajzadeh, Mir Ali; Afshar Mogaddam, Mohammad Reza

    2016-03-01

    A simple and rapid sample pretreatment technique termed low-density-solvent-based air-assisted liquid-liquid microextraction has been developed for the extraction and preconcentration of three synthetic phenolic antioxidants including butylated hydroxyanisole, butylated hydroxytoluene, and tert-butyl hydroquinone from milk samples prior to their analysis by gas chromatography with flame ionization detection. In this method, initially trichloroacetic acid as a proteins precipitation agent is added to the sample, and then it is sonicated and centrifuged. The obtained aqueous phase is removed and the analytes extracted by the proposed method using a low-density organic solvent. Some important parameters such as type and volume of extraction solvent, ionic strength, pH, and centrifugation rate and time were studied. Under the optimum conditions, enrichment factors were obtained in the range of 501-614. LODs and quantification were between 0.76-1.16 and 2.66-3.96 ng mL(-1) , respectively. This method is rapid and requires less than 15 min for sample preparation. PMID:26763356

  2. Ultrafast ionization and fragmentation of molecular silane

    SciTech Connect

    Sayres, Scott G.; Ross, Matt W.; Castleman, A. W. Jr.

    2010-09-15

    The ionization and fragmentation of molecular silane is examined here with laser intensities ranging between 7x10{sup 12} and 1x10{sup 15} W/cm{sup 2} at 624 nm. The ionization potential of silane determined using both multiphoton ionization (MPI) and tunneling ionization (TI) models agrees with the vertical ionization potential of the molecule. In addition, the application of the tunneling ionization model is extended here to the fragments of silane to determine their appearance potentials. MPI values for SiH{sub 3}{sup +}, SiH{sub 2}{sup +}, SiH{sup +}, Si{sup +}, as well as H{sub 2}{sup +} and H{sup +} are consistent with vertical potentials, whereas the TI measurements are found to be in accord with adiabatic potentials. The tunneling appearance potentials observed for the fragments H{sub 2}{sup +} and H{sup +} are lower than reported for other techniques. In fact, the appearance potential measurements for these species resulting from silane are lower than their ionization potentials. The fragmentation rate of silane is determined to be nearly 20 times larger than the ionization rate. The main precursor for producing amorphous silicon (a-Si:H) thin films, SiH{sub 3}{sup +} is the dominant fragmentation product making up roughly a third of the total ion yield, a substantial increase from other techniques.

  3. Effects of excitation and ionization in meteor trains

    NASA Astrophysics Data System (ADS)

    Jones, William; Halliday, Ian

    2001-02-01

    In a previous paper we examined the problem of the determination of the ionization coefficient β, and we now extend our analysis to the luminous efficiency τ, relating this to an excitation coefficient ζ, essentially the number of times an atom is excited during the thermalization process. We discuss the scattering processes involved and develop integral equations expressing ζ in terms of the relevant scattering cross-sections. The data available in applying these equations are (i) direct measurements of β and ζ for iron particles moving through an ionization chamber, with velocities between 18 and 46kms-1 (ii) scattering cross-sections σi and σe, for ionization and excitation on collision between Fe atoms and air molecules, measured under controlled single-atom collision in the laboratory for relative velocities between 60 and 120kms-1 (iii) theoretical calculations of the diffusion cross-section σd of iron atoms in air over the relevant velocity range. Employing an approximation in which the scattering is isotropic in the centre-of-mass frame (the random scattering approximation, RSA), we take the laboratory simulation results for the ionization and luminosity and invert the equations for β and ζ to obtain values of β0 and ζ0, the ionization and excitation probabilities at the first collision. We find that for velocities above 42kms-1 the value of ζ0 becomes greater than unity. As ζ0 is a probability, this must be incorrect, leading to the conclusion that the contribution from subsequent collisions is underestimated. This is possible if small-angle scattering is underestimated in the RSA. To investigate this we have taken the extreme case in which the trajectories of atoms are supposed to undergo no deviation at all on ionization or excitation. This now enables us to derive the ratios σiσd and σeσd and hence, using the theoretical values of the diffusion cross-section, values of σi and σe. The values so obtained appear unacceptably high and

  4. Tissue Imaging Using Nanospray Desorption Electrospray Ionization Mass Spectrometry

    SciTech Connect

    Laskin, Julia; Heath, Brandi S.; Roach, Patrick J.; Cazares, Lisa H.; Semmes, O. John

    2012-01-03

    We present the first results showing the ambient imaging of biological samples in their native environment using nanospray desorption ionization (nanoDESI) mass spectrometry. NanoDESI is an ambient pressure ionization technique that enables precise control of ionization of molecules from substrates. We demonstrate highly sensitive and robust analysis of tissue samples with high spatial resolution (<12 {mu}m) without sample preparation, which will be essential for applications in clinical diagnostics, drug discovery, molecular biology, and biochemistry.

  5. Surface-induced anisotropic orientations of interfacial ethanol molecules at air/sapphire (1-102) and ethanol/sapphire (1-102) interfaces

    SciTech Connect

    Sung, J.; Waychunas, G. A.; Shen, Y. R.

    2011-06-01

    Sum frequency vibrational spectroscopy was used to study the interfacial arrangement of ethanol molecules at the vapor/α-Al{sub 2}O{sub 3} (1{bar 1}02 ) and α-Al{sub 2}O{sub 3} (1{bar 1}02 )/ethanol liquid interfaces. The spectra in the C-H range show that ethanol molecules adsorbed from vapor onto α-Al{sub 2}O{sub 3} (1{bar 1}02 ) surface have a welldefined anisotropic arrangement following the structure of the α-Al{sub 2}O{sub 3} (1{bar 1}02 ) surface. The arrangement can be explained by the formation of two specific hydrogen bonds between the adsorbed ethanol molecule and hydroxyls on the sapphire surface. At the α-Al{sub 2}O{sub 3} (1{bar 1}02 )/ethanol liquid interface, the first ethanol monolayer assumes a similar anisotropic arrangement as in the case of an ethanol monolayer on the dry sapphire surface. The second monolayer has a rather broad orientation distribution that is azimuthally nearly isotropic, but with molecules flipped 180 degrees with respect to those in the first monolayer.

  6. Multiphoton ionization of large water clusters.

    PubMed

    Apicella, B; Li, X; Passaro, M; Spinelli, N; Wang, X

    2014-05-28

    Water clusters are multimers of water molecules held together by hydrogen bonds. In the present work, multiphoton ionization in the UV range coupled with time of flight mass spectrometry has been applied to water clusters with up to 160 molecules in order to obtain information on the electronic states of clusters of different sizes up to dimensions that can approximate the bulk phase. The dependence of ion intensities of water clusters and their metastable fragments produced by laser ionization at 355 nm on laser power density indicates a (3+1)-photon resonance-enhanced multiphoton ionization process. It also explains the large increase of ionization efficiency at 355 nm compared to that at 266 nm. Indeed, it was found, by applying both nanosecond and picosecond laser ionization with the two different UV wavelengths, that no water cluster sequences after n = 9 could be observed at 266 nm, whereas water clusters up to m/z 2000 Th in reflectron mode and m/z 3000 Th in linear mode were detected at 355 nm. The agreement between our findings on clusters of water, especially true in the range with n > 10, and reported data for liquid water supports the hypothesis that clusters above a critical dimension can approximate the liquid phase. It should thus be possible to study clusters just above 10 water molecules, for getting information on the bulk phase structure.

  7. Multiphoton ionization of large water clusters

    SciTech Connect

    Apicella, B.; Li, X.; Passaro, M.; Spinelli, N.; Wang, X.

    2014-05-28

    Water clusters are multimers of water molecules held together by hydrogen bonds. In the present work, multiphoton ionization in the UV range coupled with time of flight mass spectrometry has been applied to water clusters with up to 160 molecules in order to obtain information on the electronic states of clusters of different sizes up to dimensions that can approximate the bulk phase. The dependence of ion intensities of water clusters and their metastable fragments produced by laser ionization at 355 nm on laser power density indicates a (3+1)-photon resonance-enhanced multiphoton ionization process. It also explains the large increase of ionization efficiency at 355 nm compared to that at 266 nm. Indeed, it was found, by applying both nanosecond and picosecond laser ionization with the two different UV wavelengths, that no water cluster sequences after n = 9 could be observed at 266 nm, whereas water clusters up to m/z 2000 Th in reflectron mode and m/z 3000 Th in linear mode were detected at 355 nm. The agreement between our findings on clusters of water, especially true in the range with n > 10, and reported data for liquid water supports the hypothesis that clusters above a critical dimension can approximate the liquid phase. It should thus be possible to study clusters just above 10 water molecules, for getting information on the bulk phase structure.

  8. Electron-excited molecule interactions

    SciTech Connect

    Christophorou, L.G. Tennessee Univ., Knoxville, TN . Dept. of Physics)

    1991-01-01

    In this paper the limited but significant knowledge to date on electron scattering from vibrationally/rotationally excited molecules and electron scattering from and electron impact ionization of electronically excited molecules is briefly summarized and discussed. The profound effects of the internal energy content of a molecule on its electron attachment properties are highlighted focusing in particular on electron attachment to vibrationally/rotationally and to electronically excited molecules. The limited knowledge to date on electron-excited molecule interactions clearly shows that the cross sections for certain electron-molecule collision processes can be very different from those involving ground state molecules. For example, optically enhanced electron attachment studies have shown that electron attachment to electronically excited molecules can occur with cross sections 10{sup 6} to 10{sup 7} times larger compared to ground state molecules. The study of electron-excited molecule interactions offers many experimental and theoretical challenges and opportunities and is both of fundamental and technological significance. 54 refs., 15 figs.

  9. The galactic cosmic ray ionization rate.

    PubMed

    Dalgarno, A

    2006-08-15

    The chemistry that occurs in the interstellar medium in response to cosmic ray ionization is summarized, and a review of the ionization rates that have been derived from measurements of molecular abundances is presented. The successful detection of large abundances of H(3)(+) in diffuse clouds and the recognition that dissociative recombination of H(3)(+) is fast has led to an upward revision of the derived ionization rates. In dense clouds the molecular abundances are sensitive to the depletion of carbon monoxide, atomic oxygen, nitrogen, water, and metals and the presence of large molecules and grains. Measurements of the relative abundances of deuterated species provide information about the ion removal mechanisms, but uncertainties remain. The models, both of dense and diffuse clouds, that are used to interpret the observations may be seriously inadequate. Nevertheless, it appears that the ionization rates differ in dense and diffuse clouds and in the intercloud medium.

  10. The galactic cosmic ray ionization rate

    PubMed Central

    Dalgarno, A.

    2006-01-01

    The chemistry that occurs in the interstellar medium in response to cosmic ray ionization is summarized, and a review of the ionization rates that have been derived from measurements of molecular abundances is presented. The successful detection of large abundances of H3+ in diffuse clouds and the recognition that dissociative recombination of H3+ is fast has led to an upward revision of the derived ionization rates. In dense clouds the molecular abundances are sensitive to the depletion of carbon monoxide, atomic oxygen, nitrogen, water, and metals and the presence of large molecules and grains. Measurements of the relative abundances of deuterated species provide information about the ion removal mechanisms, but uncertainties remain. The models, both of dense and diffuse clouds, that are used to interpret the observations may be seriously inadequate. Nevertheless, it appears that the ionization rates differ in dense and diffuse clouds and in the intercloud medium. PMID:16894166

  11. Ionization potentials of seaborgium

    SciTech Connect

    Johnson, E.; Pershina, V.; Fricke, B.

    1999-10-21

    Multiconfiguration relativistic Dirac-Fock values were calculated for the first six ionization potentials of seaborgium and of the other group 6 elements. No experimental ionization potentials are available for seaborgium. Accurate experimental values are not available for all of the other ionization potentials. Ionic radii for the 4+ through 6+ ions of seaborgium are also presented. The ionization potentials and ionic radii obtained will be used to predict some physiochemical properties of seaborgium and its compounds.

  12. Matrix assisted ionization in vacuum, a sensitive and widely applicable ionization method for mass spectrometry.

    PubMed

    Trimpin, Sarah; Inutan, Ellen D

    2013-05-01

    An astonishingly simple new method to produce gas-phase ions of small molecules as well as proteins from the solid state under cold vacuum conditions is described. This matrix assisted ionization vacuum (MAIV) mass spectrometry (MS) method produces multiply charged ions similar to those that typify electrospray ionization (ESI) and uses sample preparation methods that are nearly identical to matrix-assisted laser desorption/ionization (MALDI). Unlike these established methods, MAIV does not require a laser or voltage for ionization, and unlike the recently introduced matrix assisted ionization inlet method, does not require added heat. MAIV-MS requires only introduction of a crystalline mixture of the analyte incorporated with a suitable small molecule matrix compound such as 3-nitrobenzonitrile directly to the vacuum of the mass spectrometer. Vacuum intermediate pressure MALDI sources and modified ESI sources successfully produce ions for analysis by MS with this method. As in ESI-MS, ion formation is continuous and, without a laser, little chemical background is observed. MAIV, operating from a surface offers the possibility of significantly improved sensitivity relative to atmospheric pressure ionization because ions are produced in the vacuum region of the mass spectrometer eliminating losses associated with ion transfer from atmospheric pressure to vacuum. Mechanistic aspects and potential applications for this new ionization method are discussed.

  13. Ionization Energies of Lanthanides

    ERIC Educational Resources Information Center

    Lang, Peter F.; Smith, Barry C.

    2010-01-01

    This article describes how data are used to analyze the pattern of ionization energies of the lanthanide elements. Different observed pathways of ionization between different ground states are discussed, and the effects of pairing, exchange, and orbital interactions on ionization energies of the lanthanides are evaluated. When all the above…

  14. Nanosecond Pulse Discharges and Fast Ionization Wave Discharges: Fundamental Kinetic Processes and Applications

    NASA Astrophysics Data System (ADS)

    Adamovich, Igor

    2011-10-01

    Over the last two decades, nanosecond pulse discharges and Fast Ionization Wave (FIW) discharges have been studied extensively, both theoretically and experimentally. Current interest in characterization of these discharges is driven mainly by their potential for applications such as plasma chemical fuel reforming, plasma-assisted combustion, high-speed flow control, pumping of electric discharge excited lasers, and generation of high-energy electrons. A unique capability of FIW discharges to generate significant ionization and high concentrations of excited species at high pressures and over large distances, before ionization instabilities have time to develop, is very attractive for these applications. Recent advances in laser optical diagnostics offer an opportunity of making non-intrusive, spatially and time-resolved measurements of electron density and electric field distributions in high-speed ionization wave discharges, on nanosecond time scale. Insight into FIW formation and propagation dynamics also requires development of predictive kinetic models, and their experimental validation. Although numerical kinetic models may incorporate detailed kinetics of charged and neutral species in the propagating ionization wave front (including non-local electron kinetics), analytic models are also attractive due to their capability of elucidating fundamental trends of discharge development. The talk gives an overview of recent progress in experimental characterization and kinetic modeling of nanosecond pulse and fast ionization wave discharges in nitrogen and air over a wide range of pulse repetition rates, 0.1-40 kHz. FIW discharge plasmas sustained at high pulse repetition rates are diffuse and volume filling, with most of the power coupled to the plasma behind the wave, at E/N = 200-300 Td and energy loading of 1-2 meV/molecule/pulse. The results demonstrate significant potential of large volume, diffuse, high pulse repetition rate FIW discharges for novel plasma

  15. High-Compression-Ratio; Atkinson-Cycle Engine Using Low-Pressure Direct Injection and Pneumatic-Electronic Valve Actuation Enabled by Ionization Current and Foward-Backward Mass Air Flow Sensor Feedback

    SciTech Connect

    Harold Schock; Farhad Jaberi; Ahmed Naguib; Guoming Zhu; David Hung

    2007-12-31

    This report describes the work completed over a two and one half year effort sponsored by the US Department of Energy. The goal was to demonstrate the technology needed to produce a highly efficient engine enabled by several technologies which were to be developed in the course of the work. The technologies included: (1) A low-pressure direct injection system; (2) A mass air flow sensor which would measure the net airflow into the engine on a per cycle basis; (3) A feedback control system enabled by measuring ionization current signals from the spark plug gap; and (4) An infinitely variable cam actuation system based on a pneumatic-hydraulic valve actuation These developments were supplemented by the use of advanced large eddy simulations as well as evaluations of fuel air mixing using the KIVA and WAVE models. The simulations were accompanied by experimental verification when possible. In this effort a solid base has been established for continued development of the advanced engine concepts originally proposed. Due to problems with the valve actuation system a complete demonstration of the engine concept originally proposed was not possible. Some of the highlights that were accomplished during this effort are: (1) A forward-backward mass air flow sensor has been developed and a patent application for the device has been submitted. We are optimistic that this technology will have a particular application in variable valve timing direct injection systems for IC engines. (2) The biggest effort on this project has involved the development of the pneumatic-hydraulic valve actuation system. This system was originally purchased from Cargine, a Swedish supplier and is in the development stage. To date we have not been able to use the actuators to control the exhaust valves, although the actuators have been successfully employed to control the intake valves. The reason for this is the additional complication associated with variable back pressure on the exhaust valves when

  16. Soft ionization device with characterization systems and methods of manufacture

    NASA Technical Reports Server (NTRS)

    Hartley, Frank T. (Inventor)

    2004-01-01

    Various configurations of characterization systems such as ion mobility spectrometers and mass spectrometers are disclosed that are coupled to an ionization device. The ionization device is formed of a membrane that houses electrodes therein that are located closer to one another than the mean free path of the gas being ionized. Small voltages across the electrodes generate large electric fields which act to ionize substantially all molecules passing therethrough without fracture. Methods to manufacture the mass spectrometer and ion mobility spectrometer systems are also described.

  17. Rotational And Rovibrational Energy Transfer In Electron Collisions With Molecules

    NASA Technical Reports Server (NTRS)

    Thuemmel, Helmar T.; Langhoff, Stephen R. (Technical Monitor)

    1995-01-01

    Air flows around a hypervelocity reentry vehicle undergo dissociation, rovibrational excitation and ionization. More specifically the air, initially 80% N2 and 20% O2, in the shock layer consists of species such as N, O, N2, O2, NO, N+, O+, N+, O+, NO+ and 2 free electrons. It was pointed out in multi temperature models'' that the temperature of the rotational energy modes and the gas-kinetic translational temperature are quickly equilibrated by a few collisions and rise rapidly to high temperatures as 50000K before falling off to equilibrium value of 10000K. Contrary, the electronic and vibrational temperatures state energy distributions remain low (less than 15000K) because of the slow equilibration. Electron vibrational energy transfer is thought to play a crucial role in such a ionizing flow regime since chemical reaction rates and dissociation depend strongly on the vibrational temperatures. Modeling of these flowfields in principle require the rovibrational excitation and de-excitation cross section data for average electron energies from threshold up to several eV (leV=11605.4 K). In this lecture we focus on theoretical description of rotational effects i.e. energy transfer of electrons to molecules such that the molecular rotational (vojo goes to voj) or vibrational and rotational (v(sub 0)j(sub 0) goes to vj) states are changed. Excitation and de-excitation of electronic states was discussed in a previous talk at this conference.

  18. Studying interfacial reactions of cholesterol sulfate in an unsaturated phosphatidylglycerol layer with ozone using field induced droplet ionization mass spectrometry.

    PubMed

    Ko, Jae Yoon; Choi, Sun Mi; Rhee, Young Min; Beauchamp, J L; Kim, Hugh I

    2012-01-01

    Field-induced droplet ionization (FIDI) is a recently developed ionization technique that can transfer ions from the surface of microliter droplets to the gas phase intact. The air-liquid interfacial reactions of cholesterol sulfate (CholSO(4)) in a 1-palmitoyl-2-oleoyl-sn-phosphatidylglycerol (POPG) surfactant layer with ozone (O(3)) are investigated using field-induced droplet ionization mass spectrometry (FIDI-MS). Time-resolved studies of interfacial ozonolysis of CholSO(4) reveal that water plays an important role in forming oxygenated products. An epoxide derivative is observed as a major product of CholSO(4) oxidation in the FIDI-MS spectrum after exposure of the droplet to O(3) for 5 s. The abundance of the epoxide product then decreases with continued O(3) exposure as the finite number of water molecules at the air-liquid interface becomes exhausted. Competitive oxidation of CholSO(4) and POPG is observed when they are present together in a lipid surfactant layer at the air-liquid interface. Competitive reactions of CholSO(4) and POPG with O(3) suggest that CholSO(4) is present with POPG as a well-mixed interfacial layer. Compared with CholSO(4) and POPG alone, the overall ozonolysis rates of both CholSO(4) and POPG are reduced in a mixed layer, suggesting the double bonds of both molecules are shielded by additional hydrocarbons from one another. Molecular dynamics simulations of a monolayer comprising POPG and CholSO(4) correlate well with experimental observations and provide a detailed picture of the interactions between CholSO(4), lipids, and water molecules in the interfacial region.

  19. Dynamical core polarization in strong-field ionization

    NASA Astrophysics Data System (ADS)

    Zhao, Zengxiu; Zhang, Bin; Yuan, Jianmin

    2014-05-01

    Core polarization plays an important role in both ionization and high harmonic generation processes of molecules driven by strong laser fields. With our recently developed three-dimensional time-dependent Hartree-Fock method, we investigate the orientation-dependent ionization of CO molecules. It is found that the full ionization results are in good agreement with the recent experiment. The comparisons between the full method and the single-active-orbital method show that although the core electrons are generally more tightly bound and contribute little to the total ionization yields, their dynamics cannot be ignored, which effectively modifies the behavior of electrons in the HOMO. By incorporating it into the SAO method, we identify that the dynamic core polarization plays an important role in the tunneling ionization of CO molecules, which is helpful for the future development of the tunneling ionization theory beyond the single active electron approximation. In order to further verify the role of core polarization, exact calculations are performed for the ionization of two-electron model systems by strong laser fields. The limitations of HF and the SAE are quantified and the tunneling ionization rate is shown improved with the core-polarization induced correction.

  20. Mobius Molecules

    ERIC Educational Resources Information Center

    Eckert, J. M.

    1973-01-01

    Discusses formation of chemical molecules via Mobius strip intermediates, and concludes that many special physics-chemical properties of the fully closed circular form (1) of polyoma DNA are explainable by this topological feature. (CC)

  1. Interstellar Molecules

    ERIC Educational Resources Information Center

    Solomon, Philip M.

    1973-01-01

    Radioastronomy reveals that clouds between the stars, once believed to consist of simple atoms, contain molecules as complex as seven atoms and may be the most massive objects in our Galaxy. (Author/DF)

  2. Interstellar molecules

    NASA Astrophysics Data System (ADS)

    Smith, D.

    1987-09-01

    Some 70 different molecular species have so far been detected variously in diffuse interstellar clouds, dense interstellar clouds, and circumstellar shells. Only simple (diatomic and triatomic) species exist in diffuse clouds because of the penetration of destructive UV radiations, whereas more complex (polyatomic) molecules survive in dense clouds as a result of the shielding against this UV radiation provided by dust grains. A current list of interstellar molecules is given together with a few other molecular species that have so far been detected only in circumstellar shells. Also listed are those interstellar species that contain rare isotopes of several elements. The gas phase ion chemistry is outlined via which the observed molecules are synthesized, and the process by which enrichment of the rare isotopes occurs in some interstellar molecules is described.

  3. Modeling Molecules

    NASA Technical Reports Server (NTRS)

    2000-01-01

    The molecule modeling method known as Multibody Order (N) Dynamics, or MBO(N)D, was developed by Moldyn, Inc. at Goddard Space Flight Center through funding provided by the SBIR program. The software can model the dynamics of molecules through technology which stimulates low-frequency molecular motions and properties, such as movements among a molecule's constituent parts. With MBO(N)D, a molecule is substructured into a set of interconnected rigid and flexible bodies. These bodies replace the computation burden of mapping individual atoms. Moldyn's technology cuts computation time while increasing accuracy. The MBO(N)D technology is available as Insight II 97.0 from Molecular Simulations, Inc. Currently the technology is used to account for forces on spacecraft parts and to perform molecular analyses for pharmaceutical purposes. It permits the solution of molecular dynamics problems on a moderate workstation, as opposed to on a supercomputer.

  4. Enumerating molecules.

    SciTech Connect

    Visco, Donald Patrick, Jr.; Faulon, Jean-Loup Michel; Roe, Diana C.

    2004-04-01

    This report is a comprehensive review of the field of molecular enumeration from early isomer counting theories to evolutionary algorithms that design molecules in silico. The core of the review is a detail account on how molecules are counted, enumerated, and sampled. The practical applications of molecular enumeration are also reviewed for chemical information, structure elucidation, molecular design, and combinatorial library design purposes. This review is to appear as a chapter in Reviews in Computational Chemistry volume 21 edited by Kenny B. Lipkowitz.

  5. Using Ultrafast Pulse Shaping to Probe Electronic Interference in Strong Field Ionization

    NASA Astrophysics Data System (ADS)

    Zhao, Arthur; Sándor, Péter; Rozgonyi, Tamás; Weinacht, Thomas

    2014-05-01

    We make use of shaped ultrafast laser pulses, velocity map imaging and coincidence detection to study electron dynamics in Strong Field Ionization (SFI) of small molecules. In particular, we consider the role of interference between different pathways during ionization. In one experiment, the molecule is ionized with a phase locked pulse pair. We study the ionization yield as a function of the delay and the relative phase between pulses, and interpret its variation in terms of strong field laser molecule phase matching. The authors gratefully acknowledge support from the National Science Foundation under award number 1205397 and the Hungarian National Development Agency under grant number KTIA AIK 12-1-2012-0014.

  6. Studies of atmospheric molecules by multiphoton spectroscopy

    NASA Astrophysics Data System (ADS)

    Johnson, P. M.

    1990-12-01

    Resonance ionization processes can play an important role in understanding molecules important in combustion processes. They are a reflection of the dynamic as well as the static properties of atomic and molecular species. Due to the sequential or quasisequential nature of photon absorption in resonant multiphoton events, the lifetimes of the intermediate states play an essential role in the overall cross-sections if they are short enough to be competitive with subsequent photon interactions. In molecules, this is particularly important because there are many dissociative and other radiationless pathways which can contribute to a competitive channel. Under those conditions it should be possible to obtain information about the nature of the dynamics of the intermediate state from the multiphoton ionization process. This will involve looking at not only the ionization cross-section but also other observables such as the kinetic energy of the ejected electrons and possibly the distribution of fragment ions produced in the ionization event. Whether the ionization amplitude is affected or not, the time scales of the dynamic events which alter the ionization path can vary over a large range from the femtoseconds of dissociation to the microseconds of some radiationless transitions in large molecules. When the competing channel has a time scale shorter than the laser pulse length, the kinetics of the ionization are intimately tied into the precise nature of the laser pulse. For time scales longer than the laser pulse, pump-probe ionization schemes in which one laser prepares a state while another does the ionization provide a particularly simple method for investigating the dynamics of the intermediate state. Here the author discusses examples from each of these regimes. CO2 and pyrazine are examined.

  7. Electron-Impact Ionization Cross Section Database

    National Institute of Standards and Technology Data Gateway

    SRD 107 Electron-Impact Ionization Cross Section Database (Web, free access)   This is a database primarily of total ionization cross sections of molecules by electron impact. The database also includes cross sections for a small number of atoms and energy distributions of ejected electrons for H, He, and H2. The cross sections were calculated using the Binary-Encounter-Bethe (BEB) model, which combines the Mott cross section with the high-incident energy behavior of the Bethe cross section. Selected experimental data are included.

  8. Dissociative Ionization of Pyridine by Electron Impact

    NASA Technical Reports Server (NTRS)

    Dateo, Christopher; Huo, Winifred; Kwak, Dochan (Technical Monitor)

    2002-01-01

    In order to understand the damage of biomolecules by electrons, a process important in radiation damage, we undertake a study of the dissociative ionization (DI) of pyridine (C5H5N) from the low-lying ionization channels. The methodology used is the same as in the benzene study. While no experimental DI data are available, we compare the dissociation products from our calculations with the dissociative photoionization measurements of Tixier et al. using dipole (e, e(+) ion) coincidence spectroscopy. Comparisons with the DI of benzene is also made so as to understand the difference in DI between a heterocyclic and an aromatic molecule.

  9. Analytical instruments, ionization sources, and ionization methods

    DOEpatents

    Atkinson, David A.; Mottishaw, Paul

    2006-04-11

    Methods and apparatus for simultaneous vaporization and ionization of a sample in a spectrometer prior to introducing the sample into the drift tube of the analyzer are disclosed. The apparatus includes a vaporization/ionization source having an electrically conductive conduit configured to receive sample particulate which is conveyed to a discharge end of the conduit. Positioned proximate to the discharge end of the conduit is an electrically conductive reference device. The conduit and the reference device act as electrodes and have an electrical potential maintained between them sufficient to cause a corona effect, which will cause at least partial simultaneous ionization and vaporization of the sample particulate. The electrical potential can be maintained to establish a continuous corona, or can be held slightly below the breakdown potential such that arrival of particulate at the point of proximity of the electrodes disrupts the potential, causing arcing and the corona effect. The electrical potential can also be varied to cause periodic arcing between the electrodes such that particulate passing through the arc is simultaneously vaporized and ionized. The invention further includes a spectrometer containing the source. The invention is particularly useful for ion mobility spectrometers and atmospheric pressure ionization mass spectrometers.

  10. The role of ionizing radiation in primordial organic synthesis.

    NASA Technical Reports Server (NTRS)

    Ponnamperuma, C.; Sweeney, M.

    1971-01-01

    Attempt to reveal how ionizing radiation may have been effective in producing the molecules necessary for life. In examining the sequence of events leading to the appearance of the first organisms the problem is considered in two parts: the formation of the small molecules such as amino acids, purines, pyrimidines, and carbohydrates; and the condensation of these molecules to give rise to polypeptides and polynucleotides. It is concluded that in the accumulation of organic compounds on the early earth ionizing radiation was not only a substantial part of the available energy, but was also an effective form of energy.

  11. 'Escentric' molecules.

    PubMed

    Schön, Geza

    2008-06-01

    Can a fragrance be revolutionary? In this commentary, the creation of two unusual, extravagant fine fragrances, 'escentric01' and 'molecule01', is described. In response to the fantasy components found in release notes of many recent perfume launches, both center around a single real fragrance raw material, the transparent woody aroma chemical 'Iso E Super' (1+2). The perfume 'escentric01' contains 65% of it, accompanied by Trisamber (3), red pepper, lime oil, incense and musks, while 'molecule01' consists exclusively of 'Iso E Super' (1+2). The elegant woody note lives here its own eccentric life--the revolution starts.

  12. Electron ionization of acetylene

    NASA Astrophysics Data System (ADS)

    King, Simon J.; Price, Stephen D.

    2007-11-01

    Relative partial ionization cross sections and precursor specific relative partial ionization cross sections for fragment ions formed by electron ionization of C2H2 have been measured using time-of-flight mass spectrometry coupled with a 2D ion-ion coincidence technique. We report data for the formation of H+, H2+, C2+, C+/C22+, CH +/C2H22+, CH2+, C2+, and C2H + relative to the formation of C2H2+, as a function of ionizing electron energy from 30-200eV. While excellent agreement is found between our data and one set of previously published absolute partial ionization cross sections, some discrepancies exist between the results presented here and two other recent determinations of these absolute partial ionization cross sections. We attribute these differences to the loss of some translationally energetic fragment ions in these earlier studies. Our relative precursor-specific partial ionization cross sections enable us, for the first time, to quantify the contribution to the yield of each fragment ion from single, double, and triple ionization. Analysis shows that at 50eV double ionization contributes 2% to the total ion yield, increasing to over 10% at an ionizing energy of 100eV. From our ion-ion coincidence data, we have derived branching ratios for charge separating dissociations of the acetylene dication. Comparison of our data to recent ab initio/RRKM calculations suggest that close to the double ionization potential C2H22+ dissociates predominantly on the ground triplet potential energy surface (Σg-3) with a much smaller contribution from dissociation via the lowest singlet potential energy surface (Δg1). Measurements of the kinetic energy released in the fragmentation reactions of C2H22+ have been used to obtain precursor state energies for the formation of product ion pairs, and are shown to be in good agreement with available experimental data and with theory.

  13. Effect of the degree of dissociation of molecules in a monolayer at an air/water interface on the force between the monolayer and a like-charged particle in the subphase.

    PubMed

    McNamee, Cathy E; Kappl, Michael; Butt, Hans-Juergen; Nguyen, Hang; Sato, Shinichiro; Graf, Karlheinz; Healy, Thomas W

    2012-11-26

    We used the monolayer particle interaction apparatus to measure the force between a monolayer of stearic acid or octadecanol at the air/water interface and a colloidal silica sphere. The silica sphere approached the monolayer from the aqueous subphase. The aim was to analyze how the magnitude of the charge of a deformable interface affects the interaction between that interface and a like-charged hard particle. The charge density of the stearic acid monolayer was controlled by adjusting the pH (5.8-9) and the surface pressure. The octadecanol monolayer acted as a reference; the alcohol headgroup did not dissociate between pH 5.8-9.0. Stable monolayers of dissociated stearic acid molecules were formed at the air/water interface by dissolving stearic acid into the subphase to give a saturated concentration at each pH value studied. The approach force curve showed that the electrostatic repulsion increased with an increasing degree of dissociation and therefore the charge of the monolayer. The strength of the repulsion corresponded to that measured between two like-charged hard surfaces, but the apparent range of the repulsion was larger for a deformable interface. Retracting force curves displayed a significant adhesion, whose magnitude and range depended on the surface pressure and subphase pH.

  14. Electron induced inelastic and ionization cross section for plasma modeling

    NASA Astrophysics Data System (ADS)

    Verma, Pankaj; Mahato, Dibyendu; Kaur, Jaspreet; Antony, Bobby

    2016-09-01

    The present paper reports electron impact total inelastic and ionization cross section for silicon, germanium, and tin tetrahalides at energies varying from ionization threshold of the target to 5000 eV. These cross section data over a wide energy domain are very essential to understand the physico-chemical processes involved in various environments such as plasma modeling, semiconductor etching, atmospheric sciences, biological sciences, and radiation physics. However, the cross section data on the above mentioned molecules are scarce. In the present article, we report the computation of total inelastic cross section using spherical complex optical potential formalism and the estimation of ionization cross section through a semi-empirical method. The present ionization cross section result obtained for SiCl4 shows excellent agreement with previous measurements, while other molecules have not yet been investigated experimentally. Present results show more consistent behaviour than previous theoretical estimates. Besides cross sections, we have also studied the correlation of maximum ionization cross section with the square root of the ratio of polarizability to ionization potential for the molecules with known polarizabilities. A linear relation is observed between these quantities. This correlation is used to obtain approximate polarizability volumes for SiBr4, SiI4, GeCl4, GeBr4, and GeI4 molecules.

  15. Atmospheric pressure chemical ionization source. 1. Ionization of compounds in the gas phase.

    PubMed

    Andrade, Francisco J; Shelley, Jacob T; Wetzel, William C; Webb, Michael R; Gamez, Gerardo; Ray, Steven J; Hieftje, Gary M

    2008-04-15

    A novel chemical ionization source for organic mass spectrometry is introduced. This new source uses a glow discharge in the flowing afterglow mode for the generation of excited species and ions. The direct-current gas discharge is operated in helium at atmospheric pressure; typical operating voltages and currents are around 500 V and 25 mA, respectively. The species generated by this atmospheric pressure glow discharge are mixed with ambient air to generate reagent ions (mostly ionized water clusters and NO+), which are then used for the ionization of gaseous organic compounds. A wide variety of substances, both polar and nonpolar, can be ionized. The resulting mass spectra generally show the parent molecular ion (M+ or MH+) with little or no fragmentation. Proton transfer from ionized water clusters has been identified as the main ionization pathway. However, the presence of radical molecular ions (M+) for some compounds indicates that other ionization mechanisms are also involved. The analytical capabilities of this source were evaluated with a time-of-flight mass spectrometer, and preliminary characterization shows very good stability, linearity, and sensitivity. Limits of detection in the single to tens of femtomole range are reported for selected compounds. PMID:18345693

  16. Development of Non-proximate Probe Electrospray Ionization for Real-Time Analysis of Living Animal

    PubMed Central

    Yoshimura, Kentaro; Chen, Lee Chuin; Johno, Hisashi; Nakajima, Mayutaka; Hiraoka, Kenzo; Takeda, Sen

    2014-01-01

    Ambient ionization mass spectrometry is one of the most challenging analytical tools in the field of biomedical research. We previously demonstrated that probe electrospray ionization mass spectrometry (PESI-MS) could potentially be used in the rapid diagnosis of cancer. Although this technique does not require a tedious sample pretreatment process, it was not possible for our previously reported setup to be applied to cases involving the direct sampling of tissues from living animal and large animal subjects, because there would not be enough room to accommodate the larger bodies juxtaposed to the ion inlet. To make PESI-MS more applicable for the real-time analysis of living animals, a long auxiliary ion sampling tube has been connected to the ion inlet of the mass spectrometer to allow for the collection of ions and charged droplets from the PESI source (hereafter, referred to as non-proximate PESI). Furthermore, an additional ion sampling tube was connected to a small diaphragm pump to increase the uptake rate of air carrying the ions and charged droplets to the ion inlet. This modification allows for the extended ion sampling orifice to be positioned closer to the specimens, even when they are too large to be placed inside the ionization chamber. In this study, we have demonstrated the use of non-proximate PESI-MS for the real-time analysis for biological molecules and pharmacokinetic parameters from living animals. PMID:26819892

  17. Development of Non-proximate Probe Electrospray Ionization for Real-Time Analysis of Living Animal.

    PubMed

    Yoshimura, Kentaro; Chen, Lee Chuin; Johno, Hisashi; Nakajima, Mayutaka; Hiraoka, Kenzo; Takeda, Sen

    2014-01-01

    Ambient ionization mass spectrometry is one of the most challenging analytical tools in the field of biomedical research. We previously demonstrated that probe electrospray ionization mass spectrometry (PESI-MS) could potentially be used in the rapid diagnosis of cancer. Although this technique does not require a tedious sample pretreatment process, it was not possible for our previously reported setup to be applied to cases involving the direct sampling of tissues from living animal and large animal subjects, because there would not be enough room to accommodate the larger bodies juxtaposed to the ion inlet. To make PESI-MS more applicable for the real-time analysis of living animals, a long auxiliary ion sampling tube has been connected to the ion inlet of the mass spectrometer to allow for the collection of ions and charged droplets from the PESI source (hereafter, referred to as non-proximate PESI). Furthermore, an additional ion sampling tube was connected to a small diaphragm pump to increase the uptake rate of air carrying the ions and charged droplets to the ion inlet. This modification allows for the extended ion sampling orifice to be positioned closer to the specimens, even when they are too large to be placed inside the ionization chamber. In this study, we have demonstrated the use of non-proximate PESI-MS for the real-time analysis for biological molecules and pharmacokinetic parameters from living animals.

  18. Biological Effects of Ionizing Radiation

    DOE R&D Accomplishments Database

    Ingram, M.; Mason, W. B.; Whipple, G. H.; Howland, J. W.

    1952-04-07

    This report presents a review of present knowledge and concepts of the biological effects of ionizing radiations. Among the topics discussed are the physical and chemical effects of ionizing radiation on biological systems, morphological and physiological changes observed in biological systems subjected to ionizing radiations, physiological changes in the intact animal, latent changes following exposure of biological systems to ionizing radiations, factors influencing the biological response to ionizing radiation, relative effects of various ionizing radiations, and biological dosimetry.

  19. Interstellar molecules and dense clouds.

    NASA Technical Reports Server (NTRS)

    Rank, D. M.; Townes, C. H.; Welch, W. J.

    1971-01-01

    Current knowledge of the interstellar medium is discussed on the basis of recent published studies. The subjects considered include optical identification of interstellar molecules, radio molecular lines, interstellar clouds, isotopic abundances, formation and disappearance of interstellar molecules, and interstellar probing techniques. Diagrams are plotted for the distribution of galactic sources exhibiting molecular lines, for hydrogen molecule, hydrogen atom and electron abundances due to ionization, for the densities, velocities and temperature of NH3 in the direction of Sagitarius B2, for the lower rotational energy levels of H2CO, and for temporal spectral variations in masing H2O clouds of the radio source W49. Future applications of the maser and of molecular microscopy in this field are visualized.

  20. Conceptual basis of resonance ionization spectroscopy

    SciTech Connect

    Payne, M.G.

    1984-04-01

    Resonance Ionization Spectroscopy (RIS) can b defined as a state-selective detection process in which tunable lasers are used to promote transitions from the selected state of the atoms or molecules in question to higher states, one of which will be ionized by the absorption of another photon. At least one resonance step is used in the stepwise ionization process, and it has been shown that the ionization probability of the spectroscopically selected species can nearly always be made close to unity. Since measurements of the number of photoelectrons or ions can be made very precisely and even one electron (or under vacuum conditions, one ion) can be detected, the technique can be used to make quantitative measurements of very small populations of the state-selected species. Counting of individual atoms has special meaning for detection of rare events. The ability to make saturated RIS measurements opens up a wide variety of applications to both basic and applied research. We view RIS as a specific type of multi-photon ionization in which the goal is to make quantitative measurements of quantum-selected populations in atomic or molecular systems. 16 references.

  1. Ionization of EPA contaminants in direct and dopant-assisted atmospheric pressure photoionization and atmospheric pressure laser ionization.

    PubMed

    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.

  2. 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.

  3. Ionization of EPA contaminants in direct and dopant-assisted atmospheric pressure photoionization and atmospheric pressure laser ionization.

    PubMed

    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. PMID:25828352

  4. Soft x-ray ionization induced fragmentation of glycine

    SciTech Connect

    Itälä, E.; Kooser, K.; Rachlew, E.; Huels, M. A.; Kukk, E.

    2014-06-21

    X-ray absorption commonly involves dissociative core ionization producing not only momentum correlated charged fragments but also low- and high-energy electrons capable of inducing damage in living tissue. This gives a natural motivation for studying the core ionization induced fragmentation processes in biologically important molecules such as amino acids. Here the fragmentation of amino acid glycine following carbon 1s core ionization has been studied. Using photoelectron-photoion-photoion coincidence technique, a detailed analysis on fragmentation of the sample molecule into pairs of momentum correlated cations has been carried out. The main characteristics of core ionization induced fragmentation of glycine were found to be the rupture of the C–C{sub α} bond and the presence of the CNH{sub 2}{sup +} fragment.

  5. Ionization of vitamin C in gas phase: Theoretical study.

    PubMed

    Abyar, Fatemeh; Farrokhpour, Hossein

    2016-07-01

    In this work, the gas phase ionization energies and photoelectron spectra of four important conformers of vitamin C were calculated. Symmetry adapted cluster/configuration interaction methodology employing the single and double excitation operators (SAC-CI SD-R) along with D95++(d,p) basis set were used for the calculations. Thermochemistry calculations were also performed on all possible conformers of vitamin C to find the relative stability of conformers in the gas phase. The calculated ionization bands of each conformer were assigned by calculating the contribution of natural bonding orbital (NBO) in the calculated canonical molecular orbitals involved in the ionization. SAC-CI calculations showed that the first ionization band of vitamin C is related to the π electrons of CC bond of the ring of molecule although, there is the lone electron pairs of oxygen atoms and π electrons of CO bond in the molecule. PMID:27092998

  6. Ionizing Radiation and Its Risks

    PubMed Central

    Goldman, Marvin

    1982-01-01

    Penetrating ionizing radiation fairly uniformly puts all exposed molecules and cells at approximately equal risk for deleterious consequences. Thus, the original deposition of radiation energy (that is, the dose) is unaltered by metabolic characteristics of cells and tissue, unlike the situation for chemical agents. Intensely ionizing radiations, such as neutrons and alpha particles, are up to ten times more damaging than sparsely ionizing sources such as x-rays or gamma rays for equivalent doses. Furthermore, repair in cells and tissues can ameliorate the consequences of radiation doses delivered at lower rates by up to a factor of ten compared with comparable doses acutely delivered, especially for somatic (carcinogenic) and genetic effects from x- and gamma-irradiation exposure. Studies on irradiated laboratory animals or on people following occupational, medical or accidental exposures point to an average lifetime fatal cancer risk of about 1 × 10-4 per rem of dose (100 per 106 person-rem). Leukemia and lung, breast and thyroid cancer seem more likely than other types of cancer to be produced by radiation. Radiation exposures from natural sources (cosmic rays and terrestrial radioactivity) of about 0.1 rem per year yield a lifetime cancer risk about 0.1 percent of the normally occurring 20 percent risk of cancer death. An increase of about 1 percent per rem in fatal cancer risk, or 200 rem to double the “background” risk rate, is compared with an estimate of about 100 rem to double the genetic risk. Newer data suggest that the risks for low-level radiation are lower than risks estimated from data from high exposures and that the present 5 rem per year limit for workers is adequate. PMID:6761969

  7. Diffuse, Warm Ionized Gas

    NASA Astrophysics Data System (ADS)

    Haffner, L. M.

    2002-05-01

    Over the past decade, new high-sensitivity observations have significantly advanced our knowledge of the diffuse, ionized gas in spiral galaxies. This component of the interstellar medium, often referred to as Warm Ionized Medium (WIM) or Diffuse Ionized Gas (DIG), plays an important role in the complex stellar-interstellar matter and energy cycle. In examining the distribution and physical properties of this gas, we learn not only about the conditions of the medium but also about processes providing heating and ionization in the halos of spiral galaxies. For the Milky Way, three new Hα surveys are available providing large sky coverage, arc-minute spatial resolution, and the ability to kinematically resolve this prominent optical emission line. These new, global views show that the Warm Ionized Medium of the Galaxy is ubiquitous as previously suspected, is rich with filamentary structure down to current resolution limits, and can be traced into the halo at large distances from the Galactic plane. Observations of additional optical emission lines are beginning to probe the physical conditions of the WIM. Early results suggest variations in the temperature and ionization state of the gas which are not adequately explained by Lyman continuum stellar photoionization alone. In parallel with this intensive work in the Milky Way have been numerous studies about the diffuse, ionized gas in other spiral galaxies. Here, deep, face-on spiral investigations provide some of the best maps of the global DIG distribution in a galaxy and begin to allow a probe of the local link between star formation and the powering of ionized gas. In addition, ionized gas has been traced out to impressive distances (z > 3 kpc) in edge-on spirals, revealing out large-scale changes in the physical conditions and kinematics of galactic halos.

  8. Polyatomic molecules under intense femtosecond laser irradiation.

    PubMed

    Konar, Arkaprabha; Shu, Yinan; Lozovoy, Vadim V; Jackson, James E; Levine, Benjamin G; Dantus, Marcos

    2014-12-11

    Interaction of intense laser pulses with atoms and molecules is at the forefront of atomic, molecular, and optical physics. It is the gateway to powerful new tools that include above threshold ionization, high harmonic generation, electron diffraction, molecular tomography, and attosecond pulse generation. Intense laser pulses are ideal for probing and manipulating chemical bonding. Though the behavior of atoms in strong fields has been well studied, molecules under intense fields are not as well understood and current models have failed in certain important aspects. Molecules, as opposed to atoms, present confounding possibilities of nuclear and electronic motion upon excitation. The dynamics and fragmentation patterns in response to the laser field are structure sensitive; therefore, a molecule cannot simply be treated as a "bag of atoms" during field induced ionization. In this article we present a set of experiments and theoretical calculations exploring the behavior of a large collection of aryl alkyl ketones when irradiated with intense femtosecond pulses. Specifically, we consider to what extent molecules retain their molecular identity and properties under strong laser fields. Using time-of-flight mass spectrometry in conjunction with pump-probe techniques we study the dynamical behavior of these molecules, monitoring ion yield modulation caused by intramolecular motions post ionization. The set of molecules studied is further divided into smaller sets, sorted by type and position of functional groups. The pump-probe time-delay scans show that among positional isomers the variations in relative energies, which amount to only a few hundred millielectronvolts, influence the dynamical behavior of the molecules despite their having experienced such high fields (V/Å). High level ab initio quantum chemical calculations were performed to predict molecular dynamics along with single and multiphoton resonances in the neutral and ionic states. We propose the

  9. Walking molecules.

    PubMed

    von Delius, Max; Leigh, David A

    2011-07-01

    Movement is intrinsic to life. Biologists have established that most forms of directed nanoscopic, microscopic and, ultimately, macroscopic movements are powered by molecular motors from the dynein, myosin and kinesin superfamilies. These motor proteins literally walk, step by step, along polymeric filaments, carrying out essential tasks such as organelle transport. In the last few years biological molecular walkers have inspired the development of artificial systems that mimic aspects of their dynamics. Several DNA-based molecular walkers have been synthesised and shown to walk directionally along a track upon sequential addition of appropriate chemical fuels. In other studies, autonomous operation--i.e. DNA-walker migration that continues as long as a complex DNA fuel is present--has been demonstrated and sophisticated tasks performed, such as moving gold nanoparticles from place-to-place and assistance in sequential chemical synthesis. Small-molecule systems, an order of magnitude smaller in each dimension and 1000× smaller in molecular weight than biological motor proteins or the walker systems constructed from DNA, have also been designed and operated such that molecular fragments can be progressively transported directionally along short molecular tracks. The small-molecule systems can be powered by light or chemical fuels. In this critical review the biological motor proteins from the kinesin, myosin and dynein families are analysed as systems from which the designers of synthetic systems can learn, ratchet concepts for transporting Brownian substrates are discussed as the mechanisms by which molecular motors need to operate, and the progress made with synthetic DNA and small-molecule walker systems reviewed (142 references). PMID:21416072

  10. Direct detection of enhanced ionization in CO and N2 in strong fields

    NASA Astrophysics Data System (ADS)

    Lai, Wei; Guo, Chunlei

    2014-09-01

    Enhanced ionization (EI) of molecules has been extensively studied over the past two decades as a common process in molecular dissociative ionization in strong laser fields. Direct evidence for EI has been found only in I2 and H2. However, in this work we perform a direct study of EI in CO and N2, and find enhanced ionization in an alternate dissociation channel in each of these two molecules following double ionization. Surprisingly, EI does not happen in the commonly seen dissociation channels that were previously assigned undergoing EI. Instead, EI occurs only in the alternate channels seen here with a lower kinetic-energy release.

  11. High Harmonic Spectroscopy of Multichannel Dynamics in Strong-Field Ionization

    SciTech Connect

    Mairesse, Y.; Higuet, J.; Fabre, B.; Mevel, E.; Constant, E.; Dudovich, N.; Shafir, D.; Patchkovskii, S.; Walters, Z.; Smirnova, O.; Ivanov, M. Yu.

    2010-05-28

    We perform high harmonic generation spectroscopy of aligned nitrogen molecules to characterize the attosecond dynamics of multielectron rearrangement during strong-field ionization. We use the spectrum and ellipticity of the harmonic light to reconstruct the relative phase between different ionization continua participating in the ionization, and thus determine the shape and location of the hole left in the molecule by strong-field ionization. Our interferometric technique uses transitions between the ionic states, induced by the laser field on the subcycle time scale.

  12. Signatures of bound-state-assisted nonsequential double ionization

    SciTech Connect

    Sukiasyan, Suren; McDonald, Chris; Van Vlack, Cole; Destefani, Carlos; Fennel, Thomas; Brabec, Thomas; Ivanov, Misha

    2009-07-15

    The time-dependent multiconfiguration Hartree method is optimized for intense laser dynamics and applied to nonsequential double ionization in a two-electron diatomic model molecule with two dimensions per electron. The efficiency of our method brings these calculations from the realm of large scale computation facilities to single processor machines. The resulting two-electron spectrum exhibits pronounced signatures from which the ionic bound states involved in nonsequential double ionization are retrieved with the help of a semiclassical model. A mechanism for the ionization dynamics is suggested.

  13. Mass analyzed threshold ionization spectroscopy of 4-aminobenzonitrile cation

    NASA Astrophysics Data System (ADS)

    Huang, L. C. L.; Lin, J. L.; Tzeng, W. B.

    2000-11-01

    Mass analyzed threshold ionization (MATI) and two-color resonant two-photon ionization (R2PI) methods were used to investigate the ionic properties of 4-aminobenzonitrile (4-ABN). The adiabatic ionization energy of this molecule was determined to be 66 493±4 cm -1 by the MATI spectroscopy and 66 494±7 cm -1 by the two-color R2PI spectroscopy. The active vibrations of the 4-ABN cation include the in-plane ring deformation, CC stretching, C-CN stretching, and CH bending motions. The present experimental results are well supported by our ab initio and density functional theory calculations.

  14. Ionizing radiation and orthopaedic prostheses

    NASA Astrophysics Data System (ADS)

    Rimnac, Clare M.; Kurtz, Steven M.

    2005-07-01

    Ultra high molecular weight polyethylene (UHMWPE) materials have been used successfully as one half of the bearing couple (against metallic alloys or ceramics) in total hip and total knee joint replacements for four decades. This review describes the impact of ionizing radiation (used for sterilization and for microstructural modification via crosslinking) on the performance of UHMWPE total joint replacement components. Gamma radiation sterilization in air leads to oxidative degradation of UHMWPE joint components that occurs during shelf-aging and also during in vivo use. Efforts to mitigate oxidative degradation of UHMWPE joint components include gamma radiation sterilization in inert barrier-packaging and processing treatments to reduce free radicals. Ionizing radiation (both gamma and electron-beam) has recently been used to form highly crosslinked UHMWPEs that have better adhesive and abrasive wear resistance than non-crosslinked UHMWPE, thereby potentially improving the long-term performance of total joint replacements. Along with increased wear resistance, however, there are deleterious changes to ductility and fracture resistance of UHMWPE, and an increased risk of fracture of these components remains a clinical concern.

  15. Studies of atmospheric molecules by multiphoton spectroscopy

    SciTech Connect

    Johnson, P.M.

    1991-10-01

    Carbon dioxide presents a great challenge to spectroscopy because of its propensity toward dissociation in all of its excited states. Multiphoton ionization spectroscopy is usually not applicable to the study of dissociating molecules because the dissociation competes effectively with ionization, resulting in no signal. We reasoned, however, that with high enough laser fluence, ionization could compete with dissociation in the longer lived states, exposing them for study from the continuous spectral background resulting from rapidly dissociating states. We describe the various spectroscopic and photophysical effects found through the multiphoton ionization and multiphoton photoelectron spectra. A recently developed variant of threshold ionization spectroscopy, usually called ZEKE, has shown a great deal of usefulness in providing the same information as traditional photoelectron spectroscopy but with higher resolution and much better signal-to-noise when using standard laboratory lasers. Threshold ionization techniques locate the states of an ion by scanning a light source across the ionization continuum of a neutral and somehow detecting when electrons are produced with no kinetic energy. We chose to develop our capabilities in threshold ionization spectroscopy using aromatic molecules because of their importance and because their electronic structure allows a pump-probe type of excitation scheme which avoids the use of vacuum ultraviolet laser beams. Among aromatics, the azines are noted for their small S{sub 1}-T{sub 1} energy gap which give them unique and interesting photophysical properties. We have continued our work on the multiphoton spectrum of metastable nitrogen produced by an electric discharge in supersonic beam. We have been able to assign more of the lines and simulated their rotational structure but many peaks remain unassigned.

  16. Alkali metal ionization detector

    DOEpatents

    Bauerle, James E.; Reed, William H.; Berkey, Edgar

    1978-01-01

    Variations in the conventional filament and collector electrodes of an alkali metal ionization detector, including the substitution of helical electrode configurations for either the conventional wire filament or flat plate collector; or, the substitution of a plurality of discrete filament electrodes providing an in situ capability for transferring from an operationally defective filament electrode to a previously unused filament electrode without removing the alkali metal ionization detector from the monitored environment. In particular, the helical collector arrangement which is coaxially disposed about the filament electrode, i.e. the thermal ionizer, provides an improved collection of positive ions developed by the filament electrode. The helical filament design, on the other hand, provides the advantage of an increased surface area for ionization of alkali metal-bearing species in a monitored gas environment as well as providing a relatively strong electric field for collecting the ions at the collector electrode about which the helical filament electrode is coaxially positioned. Alternatively, both the filament and collector electrodes can be helical. Furthermore, the operation of the conventional alkali metal ionization detector as a leak detector can be simplified as to cost and complexity, by operating the detector at a reduced collector potential while maintaining the sensitivity of the alkali metal ionization detector adequate for the relatively low concentration of alkali vapor and aerosol typically encountered in leak detection applications.

  17. Air Proportional Counter

    DOEpatents

    Simpson, Jr, J A

    1950-12-05

    A multiple wire counter utilizing air at atmospheric pressure as the ionizing medium and having a window of a nylon sheet of less than 0.5 mil thickness coated with graphite. The window is permeable to alpha particles so that the counter is well adapted to surveying sources of alpha radiation.

  18. Quantum control of molecular tunneling ionization in the spatiotemporal domain

    SciTech Connect

    Ohmura, Hideki; Saito, Naoaki; Morishita, Toru

    2011-06-15

    We report on a method that can control molecular photoionization in both space and time domains. The directionally asymmetric molecular tunneling ionization induced by intense (5.0 x 10{sup 13} W/cm{sup 2}) phase-controlled two-color laser pulses consisting of fundamental and second-harmonic light achieves the selective ionization of asymmetric molecules in the space domain, and manipulates the birth time and direction of photoelectron emission on an attosecond time scale. This method provides a powerful tool for tracking the quantum dynamics of photoelectrons by using phase-dependent oriented molecules as a phase reference in simultaneous ion-electron detection.

  19. Surface Ionization Gas Detection at SnO2 Surfaces

    NASA Astrophysics Data System (ADS)

    Krenkow, A.; Oberhüttinger, C.; Habauzit, A.; Kessler, M.; Göbel, J.; Müller, G.

    2009-05-01

    In surface ionization (SI) gas detection adsorbed analyte molecules are converted into ionic species at a heated solid surface and extracted into free space by an oppositely biased counter electrode. In the present work we consider the formation of positive and negative analyte gas ions at SnO2 surfaces. We find that SI leads to positive ion formation only, with the SI efficiency scaling with the ionization energy of the analyte gas molecules. Aromatic and aliphatic hydrocarbons with amine functional groups exhibit particularly high SI efficiencies.

  20. Laser plasma formation assisted by ultraviolet pre-ionization

    SciTech Connect

    Yalin, Azer P. Dumitrache, Ciprian; Wilvert, Nick; Joshi, Sachin; Shneider, Mikhail N.

    2014-10-15

    We present experimental and modeling studies of air pre-ionization using ultraviolet (UV) laser pulses and its effect on laser breakdown of an overlapped near-infrared (NIR) pulse. Experimental studies are conducted with a 266 nm beam (fourth harmonic of Nd:YAG) for UV pre-ionization and an overlapped 1064 nm NIR beam (fundamental of Nd:YAG), both having pulse duration of ∼10 ns. Results show that the UV beam produces a pre-ionized volume which assists in breakdown of the NIR beam, leading to reduction in NIR breakdown threshold by factor of >2. Numerical modeling is performed to examine the ionization and breakdown of both beams. The modeled breakdown threshold of the NIR, including assist by pre-ionization, is in reasonable agreement with the experimental results.

  1. Electroless plating of silver nanoparticles on porous silicon for laser desorption/ionization mass spectrometry

    NASA Astrophysics Data System (ADS)

    Yan, Hong; Xu, Ning; Huang, Wen-Yi; Han, Huan-Mei; Xiao, Shou-Jun

    2009-03-01

    An improved DIOS (desorption ionization on porous silicon) method for laser desorption/ionization mass spectrometry (LDI MS) by electroless plating of silver nanoparticles (AgNPs) on porous silicon (PSi) was developed. By addition of 4-aminothiophenol (4-ATP) into the AgNO3 plating solution, the plating speed can be slowed down and simultaneously 4-ATP self-assembled monolayers (SAMs) on AgNPs (4-ATP/AgNPs) were formed. Both AgNPs and 4-ATP/AgNPs coated PSi substrates present much higher stability, sensitivity and reproducibility for LDI MS than the un-treated porous silicon ones. Their shelf life in air was tested for several weeks to a month and their mass spectra still displayed the same high quality and sensitivity as the freshly prepared ones. And more 4-ATP SAMs partly play a role of matrix to increase the ionization efficiency. A small organic molecule of tetrapyridinporphyrin (TPyP), oligomers of polyethylene glycol (PEG 400 and 2300), and a peptide of oxytocin were used as examples to demonstrate the feasibility of the silver-plated PSi as a matrix-free-like method for LDI MS. This approach can obtain limits of detection to femtomoles for TPyP, subpicomoles for oxytocin, and picomoles for PEG 400 and 2300, comparable to the traditional matrix method and much better than the DIOS method. It simplifies the sample preparation as a matrix-free-like method without addition of matrix molecules and homogenizes the sample spread over the spot for better and more even mass signals.

  2. Nucleation in an Ultra Low Ionization Environment

    NASA Astrophysics Data System (ADS)

    Pedersen, J. O.; Enghoff, M. B.; Paling, S.; Svensmark, H.

    2010-12-01

    Atmospheric ions can enhance the nucleation of aerosols, as has been established by experiments, observation, and theory. In the clean marine atmosphere ionization is mainly caused by cosmic rays which in turn are controlled by the activity of the Sun, thus providing a potential link between solar activity and climate. In order to understand the effect ions may have on the production of cloud condensation nuclei the overall contribution of ion induced nucleation to the global production of secondary aerosols must be determined. One issue with determining this contribution is that several mechanisms for nucleation exist and it can be difficult to determine the relative importance of the various mechanisms in a given nucleation event when both ion induced and electrically neutral nucleation mechanisms are at work at the same time. We have carried out nucleation experiments in the Boulby Underground Laboratory, located 1100 meters below ground, thus reducing the flux of ionizing cosmic radiation by six orders of magnitude. Similarly we have reduced the gamma background by shielding the experiment in lead and copper. Finally we have used air stored for several weeks and passed through an active charcoal filter in order to reduce the Radon concentration. In this way we have been able to make nucleation experiments with very low ionizing background, meaning that we can rule out ion induced nucleation as a contributing mechanism. Our experimental setup is a 50 L electropolished stainless steel reactor at near atmospheric conditions. The chamber contains clean air with the addition of water vapor, ozone, and SO2. Using UV lights at 254 nm ozone is photolyzed, leading to the production of sulfuric acid and thus aerosols. An 18 MBq Caesium-137 gamma ray source with various amounts of lead in front allows us to alter the ionization in our chamber. By making series of nucleation bursts with varying amounts of ionizing radiation we then gauge the relative importance of ion

  3. Transverse glow discharges in supersonic air and methane flows

    SciTech Connect

    Denisova, N. V.; Postnikov, B. V.; Fomin, V. M.

    2006-03-15

    Transverse glow discharges in supersonic air and methane flows are studied both experimentally and theoretically. The experiments show that a diffuse volume discharge filling the whole cross section of the flow can easily be initiated in air, whereas a diffuse discharge in a methane flow shows a tendency to transition into a constricted mode. The electron transport coefficients (mobility and drift velocity) and the kinetic coefficients (such as collisional excitation rates of the vibrational levels of a methane molecule, as well as dissociation and ionization rates) are calculated by numerically solving the Boltzmann equation for the electron energy distribution function. The calculated coefficients are used to estimate the parameters of the plasma and the electric field in the positive column of a discharge in methane.

  4. An experimental quantification of the NOX production efficiency of energetic alpha particles in air

    NASA Astrophysics Data System (ADS)

    Rahman, Mahbubur; Cooray, Vernon; Possnert, Göran; Nyberg, Johan

    2006-07-01

    An experimental study on the production of NOX by alpha particles impact in air at atmospheric pressure is presented. A mixed radioactive source of 208Po and 209Po with an integrated activity of 9.6 MBq over a solid angle of 2π and an average alpha particle energy of 4.5 MeV was used for ionization of atmospheric air in an airtight chamber and the NOX production was measured by the chemiluminescence method. The NOX production rate is found to be about 1.2 NOX molecules per ion-pair. The NOX production efficiency per Joule of dissipated energy is calculated to be 20×1016 NOX molecules per Joule. This efficiency is comparable to that of hot laboratory sparks discharges.

  5. Dissociative Ionization of Benzene by Electron Impact

    NASA Technical Reports Server (NTRS)

    Huo, Winifred; Dateo, Christopher; Kwak, Dochan (Technical Monitor)

    2002-01-01

    We report a theoretical study of the dissociative ionization (DI) of benzene from the low-lying ionization channels. Our approach makes use of the fact that electron motion is much faster than nuclear motion and DI is treated as a two-step process. The first step is electron-impact ionization resulting in an ion with the same nuclear geometry as the neutral molecule. In the second step the nuclei relax from the initial geometry and undergo unimolecular dissociation. For the ionization process we use the improved binary-encounter dipole (iBED) model. For the unimolecular dissociation step, we study the steepest descent reaction path to the minimum of the ion potential energy surface. The path is used to analyze the probability of unimolecular dissociation and to determine the product distributions. Our analysis of the dissociation products and the thresholds of the productions are compared with the result dissociative photoionization measurements of Feng et al. The partial oscillator strengths from Feng et al. are then used in the iBED cross section calculations.

  6. Guided ionization waves: Theory and experiments

    NASA Astrophysics Data System (ADS)

    Lu, X.; Naidis, G. V.; Laroussi, M.; Ostrikov, K.

    2014-07-01

    This review focuses on one of the fundamental phenomena that occur upon application of sufficiently strong electric fields to gases, namely the formation and propagation of ionization waves-streamers. The dynamics of streamers is controlled by strongly nonlinear coupling, in localized streamer tip regions, between enhanced (due to charge separation) electric field and ionization and transport of charged species in the enhanced field. Streamers appear in nature (as initial stages of sparks and lightning, as huge structures-sprites above thunderclouds), and are also found in numerous technological applications of electrical discharges. Here we discuss the fundamental physics of the guided streamer-like structures-plasma bullets which are produced in cold atmospheric-pressure plasma jets. Plasma bullets are guided ionization waves moving in a thin column of a jet of plasma forming gases (e.g., He or Ar) expanding into ambient air. In contrast to streamers in a free (unbounded) space that propagate in a stochastic manner and often branch, guided ionization waves are repetitive and highly-reproducible and propagate along the same path-the jet axis. This property of guided streamers, in comparison with streamers in a free space, enables many advanced time-resolved experimental studies of ionization waves with nanosecond precision. In particular, experimental studies on manipulation of streamers by external electric fields and streamer interactions are critically examined. This review also introduces the basic theories and recent advances on the experimental and computational studies of guided streamers, in particular related to the propagation dynamics of ionization waves and the various parameters of relevance to plasma streamers. This knowledge is very useful to optimize the efficacy of applications of plasma streamer discharges in various fields ranging from health care and medicine to materials science and nanotechnology.

  7. Ambient ionization mass spectrometry

    NASA Astrophysics Data System (ADS)

    Lebedev, A. T.

    2015-07-01

    Ambient ionization mass spectrometry emerged as a new scientific discipline only about ten years ago. A considerable body of information has been reported since that time. Keeping the sensitivity, performance and informativity of classical mass spectrometry methods, the new approach made it possible to eliminate laborious sample preparation procedures and triggered the development of miniaturized instruments to work directly in the field. The review concerns the theoretical foundations and design of ambient ionization methods. Their advantages and drawbacks, as well as prospects for application in chemistry, biology, medicine, environmetal analysis, etc., are discussed. The bibliography includes 194 references.

  8. Effect of Near-Threshold Ionization on Electron Attachment in Gaseous Dielectrics

    NASA Astrophysics Data System (ADS)

    Sugawara, Hirotake; Ishigaki, Takuya; Hirochi, Yuuki; Sakai, Yosuke

    2004-11-01

    It has been predicted that near-threshold ionization (NTI) in a gaseous dielectric inhibits the development of electron avalanche when the gaseous dielectric has a sufficient capability for low-energy electron attachment. The NTI leaves little energy for the primary and secondary electrons involved in the ionization; thus, both electrons can be captured by dielectric gas molecules without further ionization. A computational estimation indicates that this process can occur in SF6.

  9. Communication: Electron ionization of DNA bases

    NASA Astrophysics Data System (ADS)

    Rahman, M. A.; Krishnakumar, E.

    2016-04-01

    No reliable experimental data exist for the partial and total electron ionization cross sections for DNA bases, which are very crucial for modeling radiation damage in genetic material of living cell. We have measured a complete set of absolute partial electron ionization cross sections up to 500 eV for DNA bases for the first time by using the relative flow technique. These partial cross sections are summed to obtain total ion cross sections for all the four bases and are compared with the existing theoretical calculations and the only set of measured absolute cross sections. Our measurements clearly resolve the existing discrepancy between the theoretical and experimental results, thereby providing for the first time reliable numbers for partial and total ion cross sections for these molecules. The results on fragmentation analysis of adenine supports the theory of its formation in space.

  10. Nonequilibrium ionization phenomena behind shock waves

    SciTech Connect

    Panesi, Marco; Magin, Thierry; Huo, Winifred

    2011-05-20

    An accurate investigation of the behavior of electronically excited states of atoms and molecules in the post shock relaxation zone of a trajectory point of the FIRE II flight experiment is carried out by means of a one-dimensional flow solver coupled to a collisional-radiative model. In the rapidly ionizing regime behind a strong shock wave, the high lying bound electronic states of atoms are depleted. This leads the electronic energy level populations of atoms to depart from Boltzmann distributions which strongly affects the non-equilibrium ionization process as well as the radiative signature. The importance of correct modeling of the interaction of radiation and matter is discussed showing a strong influence on the physico-chemical properties of the gas. The paper clearly puts forward the shortcomings of the simplified approach often used in literature which strongly relies on the escape factors to characterize the optical thickness of the gas.

  11. Communication: Electron ionization of DNA bases.

    PubMed

    Rahman, M A; Krishnakumar, E

    2016-04-28

    No reliable experimental data exist for the partial and total electron ionization cross sections for DNA bases, which are very crucial for modeling radiation damage in genetic material of living cell. We have measured a complete set of absolute partial electron ionization cross sections up to 500 eV for DNA bases for the first time by using the relative flow technique. These partial cross sections are summed to obtain total ion cross sections for all the four bases and are compared with the existing theoretical calculations and the only set of measured absolute cross sections. Our measurements clearly resolve the existing discrepancy between the theoretical and experimental results, thereby providing for the first time reliable numbers for partial and total ion cross sections for these molecules. The results on fragmentation analysis of adenine supports the theory of its formation in space.

  12. Communication: Electron ionization of DNA bases.

    PubMed

    Rahman, M A; Krishnakumar, E

    2016-04-28

    No reliable experimental data exist for the partial and total electron ionization cross sections for DNA bases, which are very crucial for modeling radiation damage in genetic material of living cell. We have measured a complete set of absolute partial electron ionization cross sections up to 500 eV for DNA bases for the first time by using the relative flow technique. These partial cross sections are summed to obtain total ion cross sections for all the four bases and are compared with the existing theoretical calculations and the only set of measured absolute cross sections. Our measurements clearly resolve the existing discrepancy between the theoretical and experimental results, thereby providing for the first time reliable numbers for partial and total ion cross sections for these molecules. The results on fragmentation analysis of adenine supports the theory of its formation in space. PMID:27131520

  13. Electron ionization and dissociation of aliphatic amino acids

    NASA Astrophysics Data System (ADS)

    Papp, P.; Shchukin, P.; Kočíšek, J.; Matejčík, Š.

    2012-09-01

    We present experimental and theoretical study of electron ionization and dissociative ionization to the gas phase amino acids valine, leucine, and isoleucine. A crossed electron/molecular beams technique equipped with quadrupole mass analyzer has been applied to measure mass spectra and ion efficiency curves for formation of particular ions. From experimental data the ionization energies of the molecules and the appearance energies of the fragment ions were determined. Ab initio calculations (Density Functional Theory and G3MP2 methods) were performed in order to calculate the fragmentation paths and interpret the experimental data. The experimental ionization energies of parent molecules [P]+ 8.91 ± 0.05, 8.85 ± 0.05, and 8.79 ± 0.05 eV and G3MP2 ionization energies (adiabatic) of 8.89, 8.88, and 8.81 eV were determined for valine, leucine, and isoleucine, respectively, as well as the experimental and theoretical threshold energies for dissociative ionization channels. The comparison of experimental data with calculations resulted in identification of the ions as well as the neutral fragments formed in the dissociative reactions. Around 15 mass/charge ratio fragments were identified from the mass spectra by comparison of experimental appearance energies with calculated reaction enthalpies for particular dissociative reactions.

  14. Air nonlinear dynamics initiated by ultra-intense lambda-cubic terahertz pulses

    SciTech Connect

    Shalaby, Mostafa E-mail: christoph.hauri@psi.ch; Hauri, Christoph P. E-mail: christoph.hauri@psi.ch

    2015-05-04

    We report on the measurement of the instantaneous Kerr nonlinearity and the retarded alignment of air molecules CO{sub 2}, N{sub 2}, and O{sub 2} triggered by an intense, lambda-cubic terahertz pulse, a diffraction- and transform-limited single-cycle pulse. The strong-field, impulsive low-frequency excitation (3.9 THz) leads to field-free alignment dynamics of these molecules thanks to the terahertz-induced transient dipole moments in the otherwise non-polar molecules. The strong coupling to the terahertz electric transient results in the excitation of coherent large amplitude long-living rotational states at room temperature and ambient pressure. Beyond fundamental investigations of nonlinear properties in gases, our results suggest a route towards field-free molecular alignment at laser intensity well below the ionization threshold.

  15. A Three Dimensional Beam Profile Monitor Based on Residual Gas Ionization

    SciTech Connect

    Lewis, T.A.; Shapira, D.

    1998-11-04

    A three-dimensional beam profile monitor based on tracking the ionization of the residual gas molecules in the evacuated beam pipe is described. Tracking in position and time of the ions and electrons produced in the ionization enables simultaneous position sampling in three dimensions. Special features which make it possible to sample very low beam currents were employed.

  16. Double ionization of rare-gas dimers: NeKr+e. -->. NeKr/sup 2 +/

    SciTech Connect

    Stephan, K.; Maerk, T.D.; Helm, H.

    1982-11-01

    The existence of the doubly charged dimer ion NeKr/sup 2 +/ is substantiated by electron-impact ionization of the mixed van der Waals dimer NeKr. The stability of this doubly charged molecule is discussed with the use of semiquantative potential energy curves. The electron-impact-ionization appearance potential confirms the prediction from the potential-energy curves.

  17. Alkali ionization detector

    DOEpatents

    Hrizo, John; Bauerle, James E.; Witkowski, Robert E.

    1982-01-01

    A calibration filament containing a sodium-bearing compound is included in combination with the sensing filament and ion collector plate of a sodium ionization detector to permit periodic generation of sodium atoms for the in-situ calibration of the detector.

  18. Modulated voltage metastable ionization detector

    NASA Technical Reports Server (NTRS)

    Carle, G. C.; Kojiro, D. R.; Humphrey, D. E. (Inventor)

    1985-01-01

    The output current from a metastable ionization detector (MID) is applied to a modulation voltage circuit. An adjustment is made to balance out the background current, and an output current, above background, is applied to an input of a strip chart recorder. For low level concentrations, i.e., low detected output current, the ionization potential will be at a maximum and the metastable ionization detector will operate at its most sensitive level. When the detected current from the metastable ionization detector increases above a predetermined threshold level, a voltage control circuit is activated which turns on a high voltage transistor which acts to reduce the ionization potential. The ionization potential applied to the metastable ionization detector is then varied so as to maintain the detected signal level constant. The variation in ionization potential is now related to the concentration of the constituent and a representative amplitude is applied to another input of said strip chart recorder.

  19. Ionization dynamics of small water clusters: Proton transfer rate

    NASA Astrophysics Data System (ADS)

    Tachikawa, Hiroto; Takada, Tomoya

    2016-08-01

    The surfaces of icy planets and comets are composed of frozen water (H2O), carbon dioxide (CO2), and methane (CH4). These surfaces are irradiated by solar wind and cosmic rays from the interstellar space and they cause ionization of surface molecules. In this report, the effects of ionization of cold water clusters have been investigated using a direct ab initio molecular dynamics (AIMD) method to elucidate the rate of proton transfer (PT) in cations of small water clusters (H2O)n (n = 2-7). After ionization of the water clusters, PT occurred in all the cluster cations, and dissociation of the OH radical occurred for n = 4-7. The time of PT decreased with increasing the cluster size at n = 2-5 and reached a limiting value at n = 6 and 7. The mechanism of the PT process in ionized water clusters was discussed based on the theoretical results.

  20. Molecules in the Spotlight

    SciTech Connect

    Cryan, James

    2010-01-26

    SLAC has just unveiled the world's first X-ray laser, the LCLS. This machine produces pulses of X-rays that are ten billion times brighter than those from conventional sources. One of the goals of this machine is to make movies of chemical reactions, including reactions necessary for life and reactions that might power new energy technologies. This public lecture will show the first results from the LCLS. As a first target, we have chosen nitrogen gas, the main component of the air we breathe. Using the unprecedented power of the LCLS X-rays as a blasting torch, we have created new forms of this molecule and with unique electronic arrangements. Please share with us the first insights from this new technology.

  1. Atmospheric pressure thermospray ionization using a heated microchip nebulizer.

    PubMed

    Keski-Rahkonen, Pekka; Haapala, Markus; Saarela, Ville; Franssila, Sami; Kotiaho, Tapio; Kostiainen, Risto; Auriola, Seppo

    2009-10-30

    When a standard atmospheric pressure chemical ionization (APCI) or atmospheric pressure photoionization (APPI) ion source is used without applying the corona discharge or photoirradiation, atmospheric pressure thermospray ionization (APTSI) of various compounds can be achieved. Although largely ignored, this phenomenon has recently gained interest as an alternative ionization technique. In this study, this technique is performed for the first time on a miniaturized scale using a microchip nebulizer. Sample ionization with the presented microchip-APTSI (microAPTSI) is achieved by applying only heat and gas flow to a nebulizer chip, without any other methods to promote gas-phase ionization. To evaluate the performance of the described microAPTSI setup, ionization efficiency for a set of test compounds was monitored as the microchip positioning, temperature, nebulizer gas flow rate, sample solution composition, and solvent flow rate were varied. The microAPTSI mass spectra of the test compounds were also compared to those obtained with ESI and APCI. The microAPTSI produces ESI-like spectra with low background noise, favoring the formation of protonated or deprotonated molecules of compounds that are ionizable in solution. Multiple charging of peptides without in-source fragmentation was also observed. Unlike ESI, however, the microAPTSI source can tolerate the presence of mobile phase additives like trifluoroacetic acid (TFA) without significant ion suppression. The microAPTSI source can be used with standard mass spectrometer ion source hardware, being a unique alternative to the present interfacing techniques.

  2. Laser multiphoton ionization of tetrakis(dimethylamino)ethylene.

    PubMed

    Smith, Byron H; Compton, Robert N

    2014-09-01

    The tetrakis(dimethylamino)ethylene (TDAE) molecule possesses the lowest known molecular ionization potential (<5.4 eV) and exhibits an intense Rydberg series between the first and second ionization limit (∼14 eV). The ionization of TDAE using multiphoton ionization photoelectron spectroscopy was carried out using laser light at a variety of wavelengths with a hemispherical energy analyzer. Interestingly, photoelectron signal due to direct two-photon ionization was not seen, rather ionization from a fluorescent charge-transfer state located ∼2.5 eV below the ionization limit was evident and in general agreement with a previous study. In addition, a second intense peak exists corresponding to thermal energy electrons. Measurements of the angular distribution for the electrons due to photoionization from the intermediate state are peaked along the electric field vector of the laser and the thermal electrons direction is independent of this angle. From this, we propose that the thermal peak is most likely due to thermionic emission initiated through excitation of a known long-lived Rydberg state at ∼6.5 eV. Alternately, we speculate that excitation leading to thermionic emission could result from a "collective" excitation mechanism.

  3. Electron Impact Ionization of SOx, NOx and H2 SO4 - The Aerosol Relevance

    NASA Astrophysics Data System (ADS)

    Vaishnav, B. G.; Patel, U. R.; Joshipura, K. N.; Pandya, S. H.

    2016-05-01

    This paper reports our theoretical studies on electron impact ionization of reactive molecules SOx, NOx (x = 1-3) and H2 SO4, at incident energies from threshold to 2000 eV. Motivation for this work derives from the relevance of these molecules in connection with atmospheric aerosols analysis through mass spectrometric studies and quantification of mass concentrations amongst the aerosol species. The ionization efficiency of a molecule is directly proportional to ionization cross section, which represents the efficiency on a per-molecule basis. Study of electron impact ionization cross sections of molecules, like H2 SO4, versus number of electrons in the molecule can lead to information about mass concentrations of aerosol species. We have employed in this work, the well-known spherical complex potential formalism (SCOP), which provides total elastic as well as inelastic cross sections, wherein the latter includes ionization cross sections. We have developed a method to extract ionization cross section from calculated inelastic cross section by introducing a ratio function, in a semi-empirical formalism known as CSP-ic method. For SOx and NOx targets single-centre scattering calculations are performed, while for H2 SO4, the additivity rule augmented with overlap or screening corrections, has been employed. The calculated cross sections are examined as functions of incident electron energy along with comparisons (theoretical or experimental) as available.

  4. Multiple Scattering Effects in Ionization Processes

    NASA Astrophysics Data System (ADS)

    Barrachina, R. O.

    2011-10-01

    The momentum distributions of electrons emitted in the ionization of atoms and molecules by the impact of photons or massive particles usually present interference patterns similar to those of the demonstrations with light proposed by Thomas Young more than two centuries ago. Furthermore, these cross sections also display richer structures due to the same multiple-scattering effects that are at the origin of different techniques to probe atomic aggregates and solid samples. In this talk, I will review these effects and discuss some of their most important characteristics, showing that they lead to distortions that are not fully replicated by non-scattering or even single-scattering approximations.

  5. Low-Pressure, Field-Ionizing Mass Spectrometer

    NASA Technical Reports Server (NTRS)

    Hartley, Frank; Smith, Steven

    2009-01-01

    A small mass spectrometer utilizing a miniature field ionization source is now undergoing development. It is designed for use in a variety of applications in which there are requirements for a lightweight, low-power-consumption instrument that can analyze the masses of a wide variety of molecules and ions. The device can operate without need for a high-vacuum, carrier-gas feed radioactive ionizing source, or thermal ionizer. This mass spectrometer can operate either in the natural vacuum of outer space or on Earth at any ambient pressure below 50 torr (below about 6.7 kPa) - a partial vacuum that can easily be reached by use of a small sampling pump. This mass spectrometer also has a large dynamic range - from singly charged small gas ions to deoxyribonucleic acid (DNA) fragments larger than 104 atomic mass units - with sensitivity adequate for detecting some molecules and ions at relative abundances of less than one part per billion. This instrument (see figure) includes a field ionizer integrated with a rotating-field mass spectrometer (RFMS). The field ionizer effects ionization of a type characterized as "soft" in the art because it does not fragment molecules or initiate avalanche arcing. What makes the "soft" ionization mode possible is that the distance between the ionizing electrodes is less than mean free path for ions at the maximum anticipated operating pressure, so that the ionizer always operates on the non-breakdown side of the applicable Paschen curve (a standard plot of breakdown potential on the ordinate and pressure electrode separation on the abscissa). The field ionizer in this instrument is fabricated by micromachining a submicron-thick membrane out of an electrically nonconductive substrate, coating the membrane on both sides to form electrodes, then micromachining small holes through the electrodes and membrane. Because of the submicron electrode separation, even a potential of only 1 V applied between the electrodes gives rise to an electric

  6. Picosecond laser filamentation in air

    NASA Astrophysics Data System (ADS)

    Schmitt-Sody, Andreas; Kurz, Heiko G.; Bergé, Luc; Skupin, Stefan; Polynkin, Pavel

    2016-09-01

    The propagation of intense picosecond laser pulses in air in the presence of strong nonlinear self-action effects and air ionization is investigated experimentally and numerically. The model used for numerical analysis is based on the nonlinear propagator for the optical field coupled to the rate equations for the production of various ionic species and plasma temperature. Our results show that the phenomenon of plasma-driven intensity clamping, which has been paramount in femtosecond laser filamentation, holds for picosecond pulses. Furthermore, the temporal pulse distortions in the picosecond regime are limited and the pulse fluence is also clamped. In focused propagation geometry, a unique feature of picosecond filamentation is the production of a broad, fully ionized air channel, continuous both longitudinally and transversely, which may be instrumental for many applications including laser-guided electrical breakdown of air, channeling microwave beams and air lasing.

  7. Tevatron ionization profile monitoring

    SciTech Connect

    Jansson, A.; Bowie, K.; Fitzpatrick, T.; Kwarciany, R.; Lundberg, C.; Slimmer, D.; Valerio, L.; Zagel, J.; /Fermilab

    2006-06-01

    Ionization Profile monitors have been used in almost all machines at Fermilab. However, the Tevatron presents some particular challenges with its two counter-rotating, small beams, and stringent vacuum requirements. In order to obtain adequate beam size accuracy with the small signals available, custom made electronics from particle physics experiments was employed. This provides a fast (single bunch) and dead-timeless charge integration with a sensitivity in the femto-Coulomb range, bringing the system close to the single ionization electron detection threshold. The detector itself is based on a previous Main Injector prototype, albeit with many modifications and improvements. The first detector was installed at the end of 2005, and the second detector during the spring shutdown. The ultimate goal is to continuously monitor beam size oscillations at injection, as well as the beam size evolution during ramp and squeeze. Initial results are very encouraging.

  8. Gridded electron reversal ionizer

    NASA Technical Reports Server (NTRS)

    Chutjian, Ara (Inventor)

    1993-01-01

    A gridded electron reversal ionizer forms a three dimensional cloud of zero or near-zero energy electrons in a cavity within a filament structure surrounding a central electrode having holes through which the sample gas, at reduced pressure, enters an elongated reversal volume. The resultant negative ion stream is applied to a mass analyzer. The reduced electron and ion space-charge limitations of this configuration enhances detection sensitivity for material to be detected by electron attachment, such as narcotic and explosive vapors. Positive ions may be generated by generating electrons having a higher energy, sufficient to ionize the target gas and pulsing the grid negative to stop the electron flow and pulsing the extraction aperture positive to draw out the positive ions.

  9. Hysteresis of ionization waves

    SciTech Connect

    Dinklage, A.; Bruhn, B.; Testrich, H.; Wilke, C.

    2008-06-15

    A quasi-logistic, nonlinear model for ionization wave modes is introduced. Modes are due to finite size of the discharge and current feedback. The model consists of competing coupled modes and it incorporates spatial wave amplitude saturation. The hysteresis of wave mode transitions under current variation is reproduced. Sidebands are predicted by the model and found in experimental data. The ad hoc model is equivalent to a general--so-called universal--approach from bifurcation theory.

  10. The multiphoton ionization of uranium hexafluoride

    SciTech Connect

    Armstrong, D.P. . UEO Enrichment Technical Operations Div.)

    1992-05-01

    Multiphoton ionization (MPI) time-of-flight mass spectroscopy and photoelectron spectroscopy studies of UF{sub 6} have been conducted using focused light from the Nd:YAG laser fundamental ({lambda}=1064 nm) and its harmonics ({lambda}=532, 355, or 266 nm), as well as other wavelengths provided by a tunable dye laser. The MPI mass spectra are dominated by the singly and multiply charged uranium ions rather than by the UF{sub x}{sup +} fragment ions even at the lowest laser power densities at which signal could be detected. The laser power dependence of U{sup n+} ions signals indicates that saturation can occur for many of the steps required for their ionization. In general, the doubly-charged uranium ion (U{sup 2+}) intensity is much greater than that of the singly-charged uranium ion (U{sup +}). For the case of the tunable dye laser experiments, the U{sup n+} (n = 1- 4) wavelength dependence is relatively unstructured and does not show observable resonance enhancement at known atomic uranium excitation wavelengths. The dominance of the U{sup 2+} ion and the absence or very small intensities of UF{sub x}{sup +} fragments, along with the unsaturated wavelength dependence, indicate that mechanisms may exist other than ionization of bare U atoms after the stepwise photodissociation of F atoms from the parent molecule.

  11. Nonproliferation and safeguarding via ionization detection

    SciTech Connect

    Koster, J.E.; Johnson, J.P.; Steadman, P.

    1995-05-01

    A significant signature of the presence of special nuclear material (SNM) is ionizing radiation. SNM naturally decays with the emission of alpha particles, gamma rays, and neutrons. Detecting and monitoring these emissions is an important capability for international safeguards. A new detection method collects the ions produced by such radiation in ambient air. Alpha particles in particular are specific to heavy nuclei but have very short range. The ions produced by an alpha, however, can be transported tens of meters to an ion detector. These new monitors are rugged, very sensitive, respond in real time, and in most cases are quite portable.

  12. Droplet dynamics and ionization mechanisms in desorption electrospray ionization mass spectrometry.

    PubMed

    Venter, Andre; Sojka, Paul E; Cooks, R Graham

    2006-12-15

    A droplet pickup and other mechanisms have been suggested for the ionization of biomolecules like peptides and proteins by desorption electrospray ionization. To verify this hypothesis phase Doppler particle analysis was used to study the sizes and velocities of droplets involved in DESI. It was found that impacting droplets typically have velocities of 120 m/s and average diameters of 2-4 microm. Small differences in sprayer construction influence the operating conditions at which droplets of these dimensions are produced. Under these conditions, the kinetic energy per impacting water molecule is less than 0.6 meV and sputtering through momentum transfer during collisions or ionization by other electronic processes is unlikely. Droplets arrive at the surface with velocities well below the speed of sound in common materials, thereby excluding the possibility of ionization by shockwave formation. Some droplets appear to roll along the surface, increasing contact time and presumably the amount of material that is taken up into droplets during conditions typical of the DESI experiment.

  13. Secondary electrospray ionization ion mobility spectrometry/mass spectrometry of illicit drugs.

    PubMed

    Wu, C; Siems, W F; Hill, H H

    2000-01-15

    A secondary electrospray ionization (SESI) method was developed as a nonradioactive ionization source for ion mobility spectrometry (IMS). This SESI method relied on the gas-phase interaction between charged particles created by electrospray ionization (ESI) and neutral gaseous sample molecules. Mass spectrometry (MS) was used as the detection method after ion mobility separation for ion identification. Preliminary investigations focussed on understanding the ionization process of SESI. The performance of ESI-IMS and SESI-IMS for illicit drug detection was evaluated by determining the analytical figures of merit. In general, SESI had a higher ionization efficiency for small volatile molecules compared with the electrospray method. The potential of developing a universal interface for both GC- and LC-MS with an addition stage of mobility separation was demonstrated.

  14. Electron dynamics of molecular double ionization by circularly polarized laser pulses

    SciTech Connect

    Tong, Aihong; Zhou, Yueming; Huang, Cheng; Lu, Peixiang

    2013-08-21

    Using the classical ensemble method, we have investigated double ionization (DI) of diatomic molecules driven by circularly polarized laser pulses with different internuclear distances (R). The results show that the DI mechanism changes from sequential double ionization (SDI) to nonsequential double ionization (NSDI) as the internuclear distance increases. In SDI range, the structure of the electron momentum distribution changes seriously as R increases, which indicates the sensitive dependence of the release times of the two electrons on R. For NSDI, because of the circular polarization, the ionization of the second electron is not through the well-known recollision process but through a process where the first electron ionizes over the inner potential barrier of the molecule, moves directly towards the other nucleus, and kicks out the second electron.

  15. Specific cationic emission of cisplatin following ionization by swift protons

    NASA Astrophysics Data System (ADS)

    Moretto-Capelle, Patrick; Champeaux, Jean-Philippe; Deville, Charlotte; Sence, Martine; Cafarelli, Pierre

    2016-05-01

    We have investigated collision-induced ionization and fragmentation by 100 keV protons of the radio sensitizing molecule cisplatin, which is used in cancer treatments. A large emission of HCl+ and NH2+ is observed, but surprisingly, no cationic fragments containing platinum are detected, in contrast to ionization-dissociation induced by electronic collision. Theoretical investigations show that the ionization processes take place on platinum and on chlorine atoms. We propose new ionization potentials for cisplatin. Dissociation limits corresponding to the measured fragmentation mass spectrum have been evaluated and the theoretical results show that the non-observed cationic fragments containing platinum are mostly associated with low dissociation energies. We have also investigated the reaction path for the hydrogen transfer from the NH3 group to the Cl atom, as well as the corresponding dissociation limits from this tautomeric form. Here again the cations containing platinum correspond to lower dissociation limits. Thus, the experimental results suggest that excited states, probably formed via inner-shell ionization of the platinum atom of the molecule, correlated to higher dissociation limits are favored.

  16. Laser desorption lamp ionization source for ion trap mass spectrometry.

    PubMed

    Wu, Qinghao; Zare, Richard N

    2015-01-01

    A two-step laser desorption lamp ionization source coupled to an ion trap mass spectrometer (LDLI-ITMS) has been constructed and characterized. The pulsed infrared (IR) output of an Nd:YAG laser (1064 nm) is directed to a target inside a chamber evacuated to ~15 Pa causing desorption of molecules from the target's surface. The desorbed molecules are ionized by a vacuum ultraviolet (VUV) lamp (filled with xenon, major wavelength at 148 nm). The resulting ions are stored and detected in a three-dimensional quadrupole ion trap modified from a Finnigan Mat LCQ mass spectrometer operated at a pressure of ≥ 0.004 Pa. The limit of detection for desorbed coronene molecules is 1.5 pmol, which is about two orders of magnitude more sensitive than laser desorption laser ionization mass spectrometry using a fluorine excimer laser (157 nm) as the ionization source. The mass spectrum of four standard aromatic compounds (pyrene, coronene, rubrene and 1,4,8,11,15,18,22,25-octabutoxy-29H,31H-phthalocyanine (OPC)) shows that parent ions dominate. By increasing the infrared laser power, this instrument is capable of detecting inorganic compounds. PMID:25601688

  17. Attosecond-recollision-controlled selective fragmentation of polyatomic molecules.

    PubMed

    Xie, Xinhua; Doblhoff-Dier, Katharina; Roither, Stefan; Schöffler, Markus S; Kartashov, Daniil; Xu, Huailiang; Rathje, Tim; Paulus, Gerhard G; Baltuška, Andrius; Gräfe, Stefanie; Kitzler, Markus

    2012-12-14

    Control over various fragmentation reactions of a series of polyatomic molecules (acetylene, ethylene, 1,3-butadiene) by the optical waveform of intense few-cycle laser pulses is demonstrated experimentally. We show both experimentally and theoretically that the responsible mechanism is inelastic ionization from inner-valence molecular orbitals by recolliding electron wave packets, whose recollision energy in few-cycle ionizing laser pulses strongly depends on the optical waveform. Our work demonstrates an efficient and selective way of predetermining fragmentation and isomerization reactions in polyatomic molecules on subfemtosecond time scales.

  18. Engineered Ionizable Side Chains.

    PubMed

    Cymes, Gisela D; Grosman, Claudio

    2015-01-01

    One of the great challenges of mechanistic ion-channel biology is to obtain structural information from well-defined functional states. In the case of neurotransmitter-gated ion channels, the open-channel conformation is particularly elusive owing to its transient nature and brief mean lifetime. In this Chapter, we show how the analysis of single-channel currents recorded from mutants engineered to contain single ionizable side chains in the transmembrane region can provide specific information about the open-channel conformation without any interference from the closed or desensitized conformations. The method takes advantage of the fact that the alternate binding and unbinding of protons to and from an ionizable side chain causes the charge of the protein to fluctuate by 1 unit. We show that, in mutant muscle acetylcholine nicotinic receptors (AChRs), this fluctuating charge affects the rate of ion conduction in such a way that individual proton-transfer events can be identified in a most straightforward manner. From the extent to which the single-channel current amplitude is reduced every time a proton binds, we can learn about the proximity of the engineered side chain to the lumen of the pore. And from the kinetics of proton binding and unbinding, we can calculate the side-chain's affinity for protons (pK a), and hence, we can learn about the electrostatic properties of the microenvironment around the introduced ionizable group. The application of this method to systematically mutated AChRs allowed us to identify unambiguously the stripes of the M1, M2 and M3 transmembrane α-helices that face the pore's lumen in the open-channel conformation in the context of a native membrane. PMID:26381938

  19. AIR Model Preflight Analysis

    NASA Technical Reports Server (NTRS)

    Tai, H.; Wilson, J. W.; Maiden, D. L.

    2003-01-01

    The atmospheric ionizing radiation (AIR) ER-2 preflight analysis, one of the first attempts to obtain a relatively complete measurement set of the high-altitude radiation level environment, is described in this paper. The primary thrust is to characterize the atmospheric radiation and to define dose levels at high-altitude flight. A secondary thrust is to develop and validate dosimetric techniques and monitoring devices for protecting aircrews. With a few chosen routes, we can measure the experimental results and validate the AIR model predictions. Eventually, as more measurements are made, we gain more understanding about the hazardous radiation environment and acquire more confidence in the prediction models.

  20. A positive (negative) surface ionization source concept for RIB generation

    SciTech Connect

    Alton, G.D.; Mills, G.D.

    1995-12-31

    A novel, versatile, new concept, spherical-geometry, positive (negative) surface-ionization source has been designed and fabricated which will have the capability of generating both positive- and negative-ion beams without mechanical changes to the source. The source utilizes a highly permeable, high-work-function Ir ionizer ({phi}{approximately} = 5.29 eV) for ionizing highly electropositive atoms/molecules; while for negative-surface ionization, the work function is lowered to {phi} {approximately} = 1.43 eV by continually feeding cesium vapor through the ionizer matrix. The use of Cs to effect low work function surfaces for negative ion beam generation has the potential of overcoming the chronic poisoning effects experienced with LaB{sub 6} while enhancing the probability for negative ion formation of atomic and molecular species with low to intermediate electron affinities. The flexibility of operation in either mode makes it especially attractive for RIB applications and, therefore, the source will be used as a complementary replacement for the high-temperature electron impact ionization sources presently in use at the HRIBF The design features and operational principles of the source will be described in this report.

  1. Ionization of polarized hydrogen atoms

    SciTech Connect

    Alessi, J.G.

    1983-01-01

    Methods are discussed for the production of polarized H/sup -/ ions from polarized atoms produced in ground state atomic beam sources. Present day sources use ionizers of two basic types - electron ionizers for H/sup +/ Vector production followed by double charge exchange in a vapor, or direct H/sup -/ Vector production by charge exchange of H/sup 0/ with Cs/sup 0/. Both methods have ionization efficiencies of less than 0.5%. Ionization efficiencies in excess of 10% may be obtained in the future by the use of a plasma ionizer plus charge exchange in Cs or Sr vapor, or ionization by resonant charge exchange with a self-extracted D/sup -/ beam from a ring magnetron or HCD source. 36 references, 4 figures.

  2. Nucleation in an ultra low ionization environment

    NASA Astrophysics Data System (ADS)

    Olaf Pepke Pedersen, Jens; Bødker Enghoff, Martin; Paling, Sean; Svensmark, Henrik

    2010-05-01

    Atmospheric ions can enhance the nucleation of aerosols, as has been established by experiments, observation, and theory. In the clean marine atmosphere ionization is mainly caused by cosmic rays which in turn are controlled by the activity of the Sun, thus providing a potential link between solar activity and climate. In order to understand the effect ions may have on the formation of cloud condensation nuclei and thus the Earth's radiation budget the overall contribution of ion induced nucleation to the global production of secondary aerosols must be determined. One issue with determining this contribution is that several mechanisms for nucleation exist and it can be difficult to determine the relative importance of the various mechanisms in a given nucleation event when both ion induced and electrically neutral nucleation mechanisms are at work at the same time. We have carried out nucleation experiments in the Boulby Underground Laboratory, located 1100 meters below ground, thus reducing the flux of ionizing cosmic radiation by six orders of magnitude. Similarly we have reduced the gamma background by shielding the experiment in lead and copper. Finally we have used air stored for several weeks and passed through an active charcoal filter in order to reduce the Radon concentration. In this way we have been able to make nucleation experiments with very low ionizing background, meaning that we can rule out ion induced nucleation as a contributing mechanism. Our experimental setup is a 50 L electropolished stainless steel reactor at near atmospheric conditions. The chamber contains clean air with the addition of water vapour, ozone, and sulphur dioxide. Using UV lights at 254 nm ozone is photolyzed, leading to the production of sulphuric acid and thus aerosols. An 18 MBq Caesium-137 gamma ray source with various amounts of lead in front allows us to alter the ionization in our chamber. By making series of nucleation bursts with varying amounts of ionizing

  3. Composite electron propagator methods for calculating ionization energies

    NASA Astrophysics Data System (ADS)

    Díaz-Tinoco, Manuel; Dolgounitcheva, O.; Zakrzewski, V. G.; Ortiz, J. V.

    2016-06-01

    Accurate ionization energies of molecules may be determined efficiently with composite electron-propagator (CEP) techniques. These methods estimate the results of a calculation with an advanced correlation method and a large basis set by performing a series of more tractable calculations in which large basis sets are used with simpler approximations and small basis sets are paired with more demanding correlation techniques. The performance of several CEP methods, in which diagonal, second-order electron propagator results with large basis sets are combined with higher-order results obtained with smaller basis sets, has been tested for the ionization energies of closed-shell molecules from the G2 set. Useful compromises of accuracy and computational efficiency employ complete-basis-set extrapolation for second-order results and small basis sets in third-order, partial third-order, renormalized partial-third order, or outer valence Green's function calculations. Analysis of results for vertical as well as adiabatic ionization energies leads to specific recommendations on the best use of regular and composite methods. Results for 22 organic molecules of interest in the design of photovoltaic devices, benzo[a]pyrene, Mg-octaethylporphyrin, and C60 illustrate the capabilities of CEP methods for calculations on large molecules.

  4. Composite electron propagator methods for calculating ionization energies.

    PubMed

    Díaz-Tinoco, Manuel; Dolgounitcheva, O; Zakrzewski, V G; Ortiz, J V

    2016-06-14

    Accurate ionization energies of molecules may be determined efficiently with composite electron-propagator (CEP) techniques. These methods estimate the results of a calculation with an advanced correlation method and a large basis set by performing a series of more tractable calculations in which large basis sets are used with simpler approximations and small basis sets are paired with more demanding correlation techniques. The performance of several CEP methods, in which diagonal, second-order electron propagator results with large basis sets are combined with higher-order results obtained with smaller basis sets, has been tested for the ionization energies of closed-shell molecules from the G2 set. Useful compromises of accuracy and computational efficiency employ complete-basis-set extrapolation for second-order results and small basis sets in third-order, partial third-order, renormalized partial-third order, or outer valence Green's function calculations. Analysis of results for vertical as well as adiabatic ionization energies leads to specific recommendations on the best use of regular and composite methods. Results for 22 organic molecules of interest in the design of photovoltaic devices, benzo[a]pyrene, Mg-octaethylporphyrin, and C60 illustrate the capabilities of CEP methods for calculations on large molecules. PMID:27305999

  5. Dynamic Reactive Ionization with Cluster Secondary Ion Mass Spectrometry.

    PubMed

    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.

  6. Computational study on Kerr constants of neutral and ionized gases

    NASA Astrophysics Data System (ADS)

    Sato, M.; Kumada, A.; Hidaka, K.

    2015-08-01

    In order to quantitatively examine the measurement capability of Poisson's field using electro-optic Kerr-effect (EOKE), Kerr constants of neutral molecules and ions are examined by means of first principle calculations. We have systematically computed Kerr constants of neutral molecules and ions of several molecular symmetry groups, with consistent theory level and basis sets. Computed Kerr constants of neutral molecules (N2, CO2, SF6, and CF3I) ranging across two orders of magnitudes are within 50% error of the experimental values, which are comparable to the scattering between experimental values itself. The results show that SF6 has smaller Kerr constant due to its high molecular symmetry compared to those of N2 and CO2. In contrast, CF3I has large Kerr constant due to its permanent dipole. Computed Kerr constants for anions are larger by two orders of magnitude than those of neutral molecules, probably due to the shielding effect. For cations, the opposite holds true; however, due to anisotropic polarizability, computed Kerr constants for some cations are comparable to neutral molecules, while others show smaller values. The ratio of Kerr constants of ions to those of neutral molecules are at most 102; EOKE is valid for measuring electric field in weakly ionized gas whose ionization degree is smaller than 10-3.

  7. Physics of Molecules

    NASA Astrophysics Data System (ADS)

    Williams, D.; Murdin, P.

    2000-11-01

    Many varieties of molecule have been detected in the Milky Way and in other galaxies. The processes by which these molecules are formed and destroyed are now broadly understood (see INTERSTELLAR CHEMISTRY). These molecules are important components of galaxies in two ways. Firstly, radiation emitted by molecules enables us to trace the presence of diffuse gas, to infer its physical properties and ...

  8. The particles in town air

    PubMed Central

    Ellison, J. McK.

    1965-01-01

    Particles constitute an important part of air pollution, and their behaviour when suspended in air is very different from that of gas molecules: in particular, the mechanisms by which they become deposited on surfaces are different, and consequently the methods normally used for removing particles from the air, either for sampling or for cleaning it, rely mainly on mechanisms that do not enter into the behaviour of gas molecules. These mechanisms are described, and the ways in which they affect the problems of air pollution and its measurement are discussed. ImagesFIG. 8 PMID:14315713

  9. Thiophene-Diketopyrrolopyrrole-Based Quinoidal Small Molecules as Solution-Processable and Air-Stable Organic Semiconductors: Tuning of the Length and Branching Position of the Alkyl Side Chain toward a High-Performance n-Channel Organic Field-Effect Transistor.

    PubMed

    Wang, Chao; Qin, Yunke; Sun, Yuanhui; Guan, Ying-Shi; Xu, Wei; Zhu, Daoben

    2015-07-29

    A series of thiophene-diketopyrrolopyrrole-based quinoidal small molecules (TDPPQ-2-TDPPQ-5) bearing branched alkyl chains with different side-chain lengths and varied branching positions are synthesized. Field-effect transistor (FET) measurement combined with thin-film characterization is utilized to systematically probe the influence of the side-chain length and branching position on the film microstructure, molecular packing, and, hence, charge-transport property. All of these TDPPQ derivatives show air-stable n-channel transporting behavior in spin-coated FET devices, which exhibit no significant decrease in mobility even after being stored in air for 2 months. Most notably, TDPPQ-3 exhibits an outstanding n-channel semiconducting property with electron mobilities up to 0.72 cm(2) V(-1) s(-1), which is an unprecedented value for spin-coated DPP-based n-type semiconducting small molecules. A balance of high crystallinity, satisfactory thickness uniformity and continuity, and strong intermolecular interaction accounts for the superior charge-transport characteristics of TDPPQ-3 films. Our study demonstrates that tuning the length and branching position of alkyl side chains of semiconducting molecules is a powerful strategy for achieving high FET performance. PMID:26134920

  10. Resonance Ionization, Mass Spectrometry.

    ERIC Educational Resources Information Center

    Young, J. P.; And Others

    1989-01-01

    Discussed is an analytical technique that uses photons from lasers to resonantly excite an electron from some initial state of a gaseous atom through various excited states of the atom or molecule. Described are the apparatus, some analytical applications, and the precision and accuracy of the technique. Lists 26 references. (CW)

  11. Coulomb explosion dynamics of triatomic molecules in laser pulses ranging from 7 to 200fs

    NASA Astrophysics Data System (ADS)

    Karimi, Reza; Wales, Benji; Bissone, Eric; Légaré, Francois; Kieffer, Jean-Claude; Sanderson, Joseph

    2012-11-01

    Femtosecond laser pulses from 7fs to 200fs have been used to explore the ionization process and dissociation dynamics of triatomic molecules. Time and position sensitive detection allows us to detect each fragment ion in coincidence. We observe and characterize which ionization channels are Coulombic and which are non-Coulombic, and we observe concerted and stepwise processes which involve metastable fragment ions.

  12. Single- and multi-photon ionization studies of organosulfur species

    SciTech Connect

    Cheung, Y.S.

    1999-02-12

    Accurate ionization energies (IE`s) for molecular species are used for prediction of chemical reactivity and are of fundamental importance to chemists. The IE of a gaseous molecule can be determined routinely in a photoionization or a photoelectron experiment. IE determinations made in conventional photoionization and photoelectron studies have uncertainties in the range of 3--100 meV (25--250 cm{sup {minus}1}). In the past decade, the most exciting development in the field of photoionization and photoelectron spectroscopy has been the availability of high resolution, tunable ultraviolet (UV) and vacuum ultraviolet (VUV) laser sources. The laser pulsed field ionization photoelectron (PFI-PE) scheme is currently the state-of-the-art photoelectron spectroscopic technique and is capable of providing photoelectron energy resolution close to the optical resolution. The author has focused attention on the photoionization processes of some sulfur-containing species. The studies of the photoionization and photodissociation on sulfur-containing compounds [such as CS{sub 2}, CH{sub 3}SH, CH{sub 3}SSCH{sub 3}, CH{sub 3}CH{sub 2}SCH{sub 2}CH{sub 3}, HSCH{sub 2}CH{sub 2}SH and C{sub 4}H{sub 4}S (thiophene) and sulfur-containing radicals, such as HS, CS, CH{sub 3}S, CH{sub 3}CH{sub 2}S and CH{sub 3}SS], have been the major subjects in the group because sulfur is an important species contributing to air pollution in the atmosphere. The modeling of the combustion and oxidation of sulfur compounds represents important steps for the control of both the production and the elimination of sulfur-containing pollutants. Chapter 1 is a general introduction of the thesis. Chapters 2 and 6 contain five papers published in, or accepted for publication in, academic periodicals. In Chapter 7, the progress of the construction in the laboratory of a new vacuum ultraviolet laser system equipped with a reflectron mass spectrometer is presented. Chapters 2 through 7 have been removed for separate

  13. Stagnation-point heat transfer correlation for ionized gases

    NASA Technical Reports Server (NTRS)

    Bade, W. L.

    1975-01-01

    Based on previous laminar boundary-layer solutions for argon, xenon, nitrogen, and air, it is shown that the effect of gas ionization on stagnation-point heat transfer can be correlated with the variation of the frozen Prandtl number across the boundary layer. A formula is obtained for stagnation-point heat transfer in a noble gas and is shown to be valid from the low-temperature range to the region of strong ionization. It is concluded that the considered effect can be well correlated by the 0.7 power of the Prandtl-number ratio across the boundary layer.

  14. Photostability of Organic Molecules in Circumstellar Environment

    NASA Astrophysics Data System (ADS)

    Monfredini, T.; Wolf, W.; Mendoza, E.; Rocco, M. L.; Lago, A.; Boechat-Roberty, H. M.

    2014-10-01

    Aromatic Infrared Bands, the footprint of molecules like neutral and ionic Polycyclic Aromatic Hydrocarbons (PAHs), have been observed in several astrophysical environments.We present the experimental results of the photoionization and photodissociation of the methyl-benzene (or toluene) molecule, a basic unit for the methylated PAHs, using synchrotron radiation at C1s resonance, ˜ 285 eV (soft X-ray) and time-of-flight mass-spectrometry. Absolute photoionization and photodissociation cross sections have been determined. Then the ionization and destruction rates and half-life of the toluene molecule were also obtained for the X-ray photon flux of the pre-planetary nebula CRL 618.

  15. Laser electrospray mass spectrometry of adsorbed molecules at atmospheric pressure

    NASA Astrophysics Data System (ADS)

    Brady, John J.; Judge, Elizabeth J.; Simon, Kuriakose; Levis, Robert J.

    2010-02-01

    Atmospheric pressure mass analysis of solid phase biomolecules is performed using laser electrospray mass spectrometry (LEMS). A non-resonant femtosecond duration laser pulse vaporizes native samples at atmospheric pressure for subsequent electrospray ionization and transfer into a mass spectrometer. LEMS was used to detect a complex molecule (irinotecan HCl), a complex mixture (cold medicine formulation with active ingredients: acetaminophen, dextromethorphan HBr and doxylamine succinate), and a biological building block (deoxyguanosine) deposited on steel surfaces without a matrix molecule.

  16. Photoionization of atoms and molecules. [of hydrogen, helium, and xenon

    NASA Technical Reports Server (NTRS)

    Samson, J. A. R.

    1976-01-01

    A literature review on the present state of knowledge in photoionization is presented. Various experimental techniques that have been developed to study photoionization, such as fluorescence and photoelectron spectroscopy, mass spectroscopy, are examined. Various atoms and molecules were chosen to illustrate these techniques, specifically helium and xenon atoms and hydrogen molecules. Specialized photoionization such as in positive and negative ions, excited states, and free radicals is also treated. Absorption cross sections and ionization potentials are also discussed.

  17. Frequency dependence of alternating current electrospray ionization mass spectrometry.

    PubMed

    Chetwani, Nishant; Cassou, Catherine A; Go, David B; Chang, Hsueh-Chia

    2011-04-15

    The novel effects resulting from the entrainment of low mobility ions during alternating current (ac) electrospray ionization are examined through mass spectrometry and voltage/current measurements. Curious phenomena such as pH modulation at high frequencies (>150 kHz) of an applied ac electric field are revealed and explained using simple mechanistic arguments. Current measurements are utilized to supplement these observations, and a simplified one-dimensional transient diffusion model for charge transport is used to arrive at a scaling law that provides better insight into the ac electrospray ionization process. Moreover, because of the different pathway for ion formation in comparison to direct current (dc) electrospray, ac electrospray (at frequencies >250 kHz) is shown to reduce the effects of ionization suppression in a mixture of two molecules with different surface activities. PMID:21417427

  18. Ionization of Atoms by Slow Heavy Particles, Including Dark Matter.

    PubMed

    Roberts, B M; Flambaum, V V; Gribakin, G F

    2016-01-15

    Atoms and molecules can become ionized during the scattering of a slow, heavy particle off a bound electron. Such an interaction involving leptophilic weakly interacting massive particles (WIMPs) is a promising possible explanation for the anomalous 9σ annual modulation in the DAMA dark matter direct detection experiment [R. Bernabei et al., Eur. Phys. J. C 73, 2648 (2013)]. We demonstrate the applicability of the Born approximation for such an interaction by showing its equivalence to the semiclassical adiabatic treatment of atomic ionization by slow-moving WIMPs. Conventional wisdom has it that the ionization probability for such a process should be exponentially small. We show, however, that due to nonanalytic, cusplike behavior of Coulomb functions close to the nucleus this suppression is removed, leading to an effective atomic structure enhancement. We also show that electron relativistic effects actually give the dominant contribution to such a process, enhancing the differential cross section by up to 1000 times.

  19. Ionization of Atoms by Slow Heavy Particles, Including Dark Matter

    NASA Astrophysics Data System (ADS)

    Roberts, B. M.; Flambaum, V. V.; Gribakin, G. F.

    2016-01-01

    Atoms and molecules can become ionized during the scattering of a slow, heavy particle off a bound electron. Such an interaction involving leptophilic weakly interacting massive particles (WIMPs) is a promising possible explanation for the anomalous 9 σ annual modulation in the DAMA dark matter direct detection experiment [R. Bernabei et al., Eur. Phys. J. C 73, 2648 (2013)]. We demonstrate the applicability of the Born approximation for such an interaction by showing its equivalence to the semiclassical adiabatic treatment of atomic ionization by slow-moving WIMPs. Conventional wisdom has it that the ionization probability for such a process should be exponentially small. We show, however, that due to nonanalytic, cusplike behavior of Coulomb functions close to the nucleus this suppression is removed, leading to an effective atomic structure enhancement. We also show that electron relativistic effects actually give the dominant contribution to such a process, enhancing the differential cross section by up to 1000 times.

  20. Modeling ionization cross sections: Two decades of dreams come true

    NASA Astrophysics Data System (ADS)

    Kim, Yong-Ki

    1996-03-01

    Modeling of differential and total ionization cross sections by electron impact is reviewed. A new theoretical model that does not depend on any empirical or arbitrary parameters is described. The prototype of this new model was proposed by Rudd and was originally based on the binary-encounter theory. The model has been improved by replacing a part of the binary-encounter theory with the dipole contribution as prescribed by the Bethe theory. The current model, henceforth referred to as the binary-encounter-dipole (BED) model, reproduces known singly differential and total ionization cross sections for small atoms and molecules accurately. The possibility of extending the BED theory to doubly differential cross sections as well as to proton-impact ionization cross sections is discussed.

  1. Associative ionization reactions involving excited atoms in nitrogen plasma

    SciTech Connect

    Popov, N. A.

    2009-05-15

    A model of kinetic processes in gas-discharge plasmas of pure nitrogen and its mixtures with nitrogen oxide and oxygen is presented. A distinctive feature of the model is that it includes associative ionization reactions involving N({sup 2}P) electronically excited atoms. Taking into account these processes allows one to explain both the anomalously slow decay of gas-discharge nitrogen plasma and the increase in the electron density in the region of the so-called pink afterglow in nitrogen. The possibility of substantially accelerating secondary ionization by adding NO molecules to a partially dissociated nitrogen is demonstrated. It is shown that such acceleration is caused by the associative ionization reaction N({sup 2}P) + O({sup 3}P) {yields} e + NO{sup +}. The calculated results agree well with available experimental data.

  2. Ionized cluster beam deposition

    NASA Astrophysics Data System (ADS)

    Kirkpatrick, A. R.

    1983-11-01

    Ionized Cluster Beam (ICB) deposition, a new technique originated by Takagi of Kyoto University in Japan, offers a number of unique capabilities for thin film metallization as well as for deposition of active semiconductor materials. ICB allows average energy per deposited atom to be controlled and involves impact kinetics which result in high diffusion energies of atoms on the growth surface. To a greater degree than in other techniques, ICB involves quantitative process parameters which can be utilized to strongly control the characteristics of films being deposited. In the ICB deposition process, material to be deposited is vaporized into a vacuum chamber from a confinement crucible at high temperature. Crucible nozzle configuration and operating temperature are such that emerging vapor undergoes supercondensation following adiabatic expansion through the nozzle.

  3. Ionizing radiation detector

    DOEpatents

    Thacker, Louis H.

    1990-01-01

    An ionizing radiation detector is provided which is based on the principle of analog electronic integration of radiation sensor currents in the sub-pico to nano ampere range between fixed voltage switching thresholds with automatic voltage reversal each time the appropriate threshold is reached. The thresholds are provided by a first NAND gate Schmitt trigger which is coupled with a second NAND gate Schmitt trigger operating in an alternate switching state from the first gate to turn either a visible or audible indicating device on and off in response to the gate switching rate which is indicative of the level of radiation being sensed. The detector can be configured as a small, personal radiation dosimeter which is simple to operate and responsive over a dynamic range of at least 0.01 to 1000 R/hr.

  4. Ionized cluster beam deposition

    NASA Technical Reports Server (NTRS)

    Kirkpatrick, A. R.

    1983-01-01

    Ionized Cluster Beam (ICB) deposition, a new technique originated by Takagi of Kyoto University in Japan, offers a number of unique capabilities for thin film metallization as well as for deposition of active semiconductor materials. ICB allows average energy per deposited atom to be controlled and involves impact kinetics which result in high diffusion energies of atoms on the growth surface. To a greater degree than in other techniques, ICB involves quantitative process parameters which can be utilized to strongly control the characteristics of films being deposited. In the ICB deposition process, material to be deposited is vaporized into a vacuum chamber from a confinement crucible at high temperature. Crucible nozzle configuration and operating temperature are such that emerging vapor undergoes supercondensation following adiabatic expansion through the nozzle.

  5. Positive streamers in air of varying density: experiments on the scaling of the excitation density

    NASA Astrophysics Data System (ADS)

    Dubrovin, D.; Nijdam, S.; Clevis, T. T. J.; Heijmans, L. C. J.; Ebert, U.; Yair, Y.; Price, C.

    2015-02-01

    Streamers are rapidly extending ionized finger-like structures that dominate the initial breakdown of large gas volumes in the presence of a sufficiently strong electric field. Their macroscopic parameters are described by simple scaling relations, where the densities of electrons and of excited molecules in the active streamer front scale as the square of the density of the neutral gas. In this work we estimate the absolute density of nitrogen molecules, excited to the C3Πu state that emit photons in the 2P-N2 band, by radiometrically calibrated short exposure intensified imaging. We test several pressures (100, 200 and 400 mbar) in artificial air at room temperature. Our results provide a first confirmation for the scaling of the density of excited species with the gas density. The method proposed here is particularly suitable to characterize the excitation densities in sprite streamers in the atmosphere.

  6. Amorphous silicon ionizing particle detectors

    DOEpatents

    Street, Robert A.; Mendez, Victor P.; Kaplan, Selig N.

    1988-01-01

    Amorphous silicon ionizing particle detectors having a hydrogenated amorphous silicon (a--Si:H) thin film deposited via plasma assisted chemical vapor deposition techniques are utilized to detect the presence, position and counting of high energy ionizing particles, such as electrons, x-rays, alpha particles, beta particles and gamma radiation.

  7. Amorphous silicon ionizing particle detectors

    DOEpatents

    Street, R.A.; Mendez, V.P.; Kaplan, S.N.

    1988-11-15

    Amorphous silicon ionizing particle detectors having a hydrogenated amorphous silicon (a--Si:H) thin film deposited via plasma assisted chemical vapor deposition techniques are utilized to detect the presence, position and counting of high energy ionizing particles, such as electrons, x-rays, alpha particles, beta particles and gamma radiation. 15 figs.

  8. Air Heating Associated with Transient Luminous Events

    NASA Astrophysics Data System (ADS)

    Riousset, J. A.; Pasko, V. P.; Bourdon, A.

    2009-12-01

    caused by streamers in transient luminous events. In this talk we will discuss scaling properties of physical processes involved in the air heating in streamer channels as a function of air pressure and will report the most recent results from a model developed for investigation of effective time scales of air heating in streamer channels. The model explicitly includes energy input in fast heating, vibrational excitation of nitrogen molecules, the vibrational-translational relaxation processes, and accounts for the effects of gains in electron energy in collisions with vibrationally excited nitrogen molecules on the rate constants of ionization and dissociative attachment processes [Belinov and Naidis, J. Phys. D: Appl. Phys., 36, 1834, 2003, and references therein]. We will discuss performance of different models proposed in recent literature for positive ion chemistry, including O2+, O4+ and O2+N2 ions.

  9. Modeling impact ionization of precipitating particles in the upper and middle atmosphere

    NASA Astrophysics Data System (ADS)

    Mishev, Alexander; Usoskin, Ilya; Artamonov, Anton

    2016-07-01

    An extension of the cosmic ray ionization model CRAC:EPII (Cosmic Ray Atmospheric Cascade: Electron Precipitation Induced Ionization) is presented. It aims computation of electron impact ionization in the atmosphere. The CRAC:EPII is based on Monte Carlo simulations of electron propagation and interaction with matter, namely atmospheric molecules. It explicitly considers various physical process, namely pair production, Compton scattering, generation of Bremsstrahlung photons, photo-ionization, annihilation of positrons, multiple scattering as well as energy deposit and accordingly ionization. Propagation of precipitating electrons and their interactions with atmospheric molecules is modelled with the the PLANETOCOSMICS code. The atmospheric model NRLMSISE 2000 is used. The yield functions for computation of electron impact ionization are presented. A quantitative comparison with a parameterization driven model of the atmospheric ionization induced by precipitating electronsis is carried out. A good agreement is demonstrated. Several example electron spectra based on balloon-born measurements are used as input in the model in order to compute ion production in the upper and middle atmosphere. An updated ionization yield function by primary cosmic ray protons in the upper/middle atmosphere is also presented. Several examples of ion production in the upper and middle atmosphere due to precipitating particles are shown.

  10. Laser-initiated Coulomb explosion imaging of small molecules

    NASA Astrophysics Data System (ADS)

    Brichta, Jean-Paul

    Momentum vectors of fragment ions produced by the Coulomb explosion of COz+2 (z = 3 - 6) and CSz+2 (z = 3 - 13) in an intense laser field (˜50 fs, 1 x 1015 W/cm2) are determined by the triple coincidence imaging technique. The molecular structure from symmetric and asymmetric explosion channels is reconstructed from the measured momentum vectors using a novel simplex algorithm that can be extended to study larger molecules. Physical parameters such as bend angle and bond lengths are extracted from the data and are qualitatively described using an enhanced ionization model that predicts the laser intensity required for ionization as a function of bond length using classical, over the barrier arguments. As a way of going beyond the classical model, molecular ionization is examined using a quantum-mechanical, wave function modified ADK method. The ADK model is used to calculate the ionization rates of H2, N 2 and CO2 as a function of initial vibrational level of the molecules. A strong increase in the ionization rate, with vibrational level, is found for H2, while N2 and CO2 show a lesser increase. The prospects for using ionization rates as a diagnostic for vibrational level population are assessed.

  11. Ionization detection system for aerosols

    DOEpatents

    Jacobs, Martin E.

    1977-01-01

    This invention relates to an improved smoke-detection system of the ionization-chamber type. In the preferred embodiment, the system utilizes a conventional detector head comprising a measuring ionization chamber, a reference ionization chamber, and a normally non-conductive gas triode for discharging when a threshold concentration of airborne particulates is present in the measuring chamber. The improved system utilizes a measuring ionization chamber which is modified to minimize false alarms and reductions in sensitivity resulting from changes in ambient temperature. In the preferred form of the modification, an annular radiation shield is mounted about the usual radiation source provided to effect ionization in the measuring chamber. The shield is supported by a bimetallic strip which flexes in response to changes in ambient temperature, moving the shield relative to the source so as to vary the radiative area of the source in a manner offsetting temperature-induced variations in the sensitivity of the chamber.

  12. X-ray FEL induced multiphton ionization and molecular dissociation

    NASA Astrophysics Data System (ADS)

    Fang, Li

    2014-05-01

    X-ray Free electron lasers (FELs) enable multiphoton absorption at the core levels which is not possible with conventional light sources. Multiphoton ionization and the subsequent core-hole states relaxation lead to dramatic dynamics of the molecules. We present our experimental as well as theoretical results on multiphoton ionization and molecular fragmentation dynamics with the Linac Coherent Light Source (LCLS) at SLAC National Laboratory. We investigated simple diatomic system, N2 molecules, where we used multiphoton ionization as an internal clock for imaging the dynamics in time and the internuclear separation domain. We observed the modification of the ionization dynamic by varying the x-ray beam parameters and the effect of the spatial distribution on the ionization. We also investigated a complex system, C60, where we developed a full model to simulate the multiphoton ionization that results in various molecular ions and atomic carbon ions up to charge 6+. The calculation agrees well with our experimental results in ion kinetic energy distribution and charge state distribution. Moreover, our model provides further insights into the photoionization and dissociation dynamics as a function of time and molecular size. This work was supported by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences. Thank T. Osipov, B. Murphy, Z. Jurek, S.-K. Son, R. Santra, and N. Berrah, M. Hoener, O. Gessner, F. Tarantelli, S.T. Pratt, O. Kornilov, C. Buth, M. Güehr, E. Kanter, C. Bostedt, J. D. Bozek, P. H. Bucksbaum, M. Chen, R. Coffee, J. Cryan, L. DiMauro, M. Glownia, E. Kukk, S.R. Leone, L. Avaldi, P. Bolognesi, J. Eland, J. Farrell, R. Feifel, L. Frasinski, D.T. Ha, K. Hoffmann, B. McFarland, C. Miron, M. Mucke, R. Squibb, K. Ueda for their contributions to this work.

  13. Few-Photon Double Ionization of He and H2

    NASA Astrophysics Data System (ADS)

    Jiang, Wei-Chao; Xiong, Wei-Hao; Geng, Ji-Wei; Gong, Qihuang; Peng, Liang-You

    Studies on the few-photon double ionization of helium atom and hydrogen molecule have fundamental significances on the electronic correlation. In recent years, many theoretical efforts have been put on the numerical solution to the corresponding time-dependent Schrödinger equation (TDSE) in the real space. These ab initio calculations promise to produce accurate numerical results that can be directly compared with the experimental observations. With further developments of free electron lasers (FEL) and high harmonic generation (HHG) sources and relevant coincidence measurement techniques, these theoretical predictions have a greater chance to be experimentally checked. In this chapter, we will first introduce our numerical methodologies to solve the TDSE and then provide some numerical results for the few-photon double ionization of helium atom and hydrogen molecule. At the same time, existing experimental results will be reviewed briefly.

  14. Fragmentation pathways of tungsten hexacarbonyl clusters upon electron ionization

    NASA Astrophysics Data System (ADS)

    Neustetter, M.; Jabbour Al Maalouf, E.; Limão-Vieira, P.; Denifl, S.

    2016-08-01

    Electron ionization of neat tungsten hexacarbonyl (W(CO)6) clusters has been investigated in a crossed electron-molecular beam experiment coupled with a mass spectrometer system. The molecule is used for nanofabrication processes through electron beam induced deposition and ion beam induced deposition techniques. Positive ion mass spectra of W(CO)6 clusters formed by electron ionization at 70 eV contain the ion series of the type W(CO)n+ (0 ≤ n ≤ 6) and W2(CO)n+ (0 ≤ n ≤ 12). In addition, a series of peaks are observed and have been assigned to WC(CO)n+ (0 ≤ n ≤ 3) and W2C(CO)n+ (0 ≤ n ≤ 10). A distinct change of relative fragment ion intensity can be observed for clusters compared to the single molecule. The characteristic fragmentation pattern obtained in the mass spectra can be explained by a sequential decay of the ionized organometallic, which is also supported by the study of the clusters when embedded in helium nanodroplets. In addition, appearance energies for the dissociative ionization channels for singly charged ions have been estimated from experimental ion efficiency curves.

  15. Fragmentation pathways of tungsten hexacarbonyl clusters upon electron ionization.

    PubMed

    Neustetter, M; Jabbour Al Maalouf, E; Limão-Vieira, P; Denifl, S

    2016-08-01

    Electron ionization of neat tungsten hexacarbonyl (W(CO)6) clusters has been investigated in a crossed electron-molecular beam experiment coupled with a mass spectrometer system. The molecule is used for nanofabrication processes through electron beam induced deposition and ion beam induced deposition techniques. Positive ion mass spectra of W(CO)6 clusters formed by electron ionization at 70 eV contain the ion series of the type W(CO)n (+) (0 ≤ n ≤ 6) and W2(CO)n (+) (0 ≤ n ≤ 12). In addition, a series of peaks are observed and have been assigned to WC(CO)n (+) (0 ≤ n ≤ 3) and W2C(CO)n (+) (0 ≤ n ≤ 10). A distinct change of relative fragment ion intensity can be observed for clusters compared to the single molecule. The characteristic fragmentation pattern obtained in the mass spectra can be explained by a sequential decay of the ionized organometallic, which is also supported by the study of the clusters when embedded in helium nanodroplets. In addition, appearance energies for the dissociative ionization channels for singly charged ions have been estimated from experimental ion efficiency curves. PMID:27497555

  16. Chemical Recycling of Molecules in Cometary Comae

    NASA Astrophysics Data System (ADS)

    Boice, Daniel C.; Kawakita, Hideyo; Shinnaka, Yoshiharu; Kobayashi, Hitomi

    2015-08-01

    Modeling is essential to understand the important physical and chemical processes that occur in cometary comae, especially the relationship between native and sibling molecules, such as, HCN and CN. Photochemistry is a major source of ions and electrons that further initiate key gas-phase reactions, leading to the plethora of molecules and atoms observed in comets. The effects of photoelectrons that react via impacts are important to the overall ionization in the inner coma. We have found that many molecules undergo protonation reactions with primarily water, followed by electron recombination resulting in the original molecules in a vibrationally excited state. These excited molecules spontaneously emit photons back to the ground state. We identify this series of reactions as chemical “recycling.” We discuss the importance of this mechanism for HCN, NH3, and water in comets. We also identify other relevant processes in the collision-dominated, inner coma of a comet within a global modeling framework to better understand observations and in situ measurements of cometary species, especially relationships between native and sibling molecules for the Rosetta Mission to Comet 67P/Churyumov-Gerasimenko.Acknowledgements: We appreciate support from the NSF Planetary Astronomy Program under Grant No. 0908529. This program is partially supported by the MEXT Supported Program for the Strategic Research Foundation at Private Universities, 2014-2018.

  17. Vibrational Cooling of Photoassociated Homonuclear Cold Molecules

    NASA Astrophysics Data System (ADS)

    Passagem, Henry; Ventura, Paulo; Tallant, Jonathan; Marcassa, Luis

    2015-05-01

    In this work, we produce vibrationally cold homonuclear Rb molecules using spontaneous optical pumping. The vibrationally cooled molecules are produced in three steps. In the first step, we use a photoassociation laser to produce molecules in high vibrational levels of the singlet ground state. Then in a second step, a 50 W broadband laser at 1071 nm, which bandwidth is about 2 nm, is used to transfer the molecules to lower vibrational levels via optical pumping through the excited state. This process transfers the molecules from vibrational levels around ν ~= 113 to a distribution of levels below ν = 35 . The molecules can be further cooled using a broadband light source near 685 nm. In order to obtain such broadband source, we have used a 5 mW superluminescent diode, which is amplified in a tapered amplifier using a double pass configuration. After the amplification, the spectrum is properly shaped and we end up with about 90 mW distributed in the 682-689 nm range. The final vibrational distribution is probed using resonance-enhanced multiphoton ionization with a pulsed dye laser near 670 nm operating at 4KHz. The results are presented and compared with theoretical simulations. This work was supported by Fapesp and INCT-IQ.

  18. Electron-impact ionization and dissociative ionization of biomolecules

    NASA Astrophysics Data System (ADS)

    Huo, Winifred

    2006-05-01

    Oxidative damages by ionizing radiation are the source of radiation-induced damages to human health. It is recognized that secondary electrons play a role in the damage process, particularly important is the damage of DNA by electrons, potentially leading to mutagenesis. The damage can be direct, by creating a DNA lesion, or indirect, by producing radicals that attack the DNA. Molecular-level study of electron interaction with DNA provides information on the damage pathways and dominant mechanisms. This investigation focuses on ionization and dissociative ionization (DI) of DNA fragments by electron-impact. For ionization we use the improved binary-encounter dipole (iBED) model [W.M. Huo, Phys. Rev. A64, 042719-1 (2001)]. For DI it is assumed that electron motion is much faster than nuclear motion, allowing DI to be treated as a two-step process and the DI cross section given by the product of the ionization cross section and dissociation probability. The ionization study covers DNA bases, sugar phosphate backbone, and nucleotides. An additivity principle is observed. For example, the sum of the ionization cross sections of the separate deoxyribose and phosphate fragments is in close agreement with the C3'- and C5'-deoxyribose-phospate cross sections, differing by less than 5%. The result implies that certain properties of the DNA, like the total ionization cross section, are localized properties and an additivity principle may apply. This allows us to obtain properties of a larger molecular system built up from the results of smaller subsystem fragments. The DI of guanine and cytosine has been studied. For guanine, a proton is produced from the channel where the ionized electron originates from a molecular orbital with significant charge density along the N(1)-H bond. The interaction of the proton with cytosine was also studied.

  19. Air Pollution

    MedlinePlus

    Air pollution is a mixture of solid particles and gases in the air. Car emissions, chemicals from factories, ... Ozone, a gas, is a major part of air pollution in cities. When ozone forms air pollution, it's ...

  20. Atmospheric fate of non-volatile and ionizable compounds.

    PubMed

    Franco, Antonio; Hauschild, Michael; Jolliet, Olivier; Trapp, Stefan

    2011-11-01

    A modified version of the Multimedia Activity Model for Ionics MAMI, including two-layered atmosphere, air-water interface partitioning, intermittent rainfall and variable cloud coverage was developed to simulate the atmospheric fate of ten low volatility or ionizable organic chemicals. Probabilistic simulations describing the uncertainty of substance and environmental input properties were run to evaluate the impact of atmospheric parameters, ionization and air-water (or air-ice) interface enrichment. The rate of degradation and the concentration of OH radicals, the duration of dry and wet periods, and the parameters describing air-water partitioning (K(AW) and temperature) and ionization (pK(a) and pH) are the key parameters determining the potential for long range transport. Wet deposition is an important removal process, but its efficiency is limited, primarily by the duration of the dry period between precipitation events. Given the underlying model assumptions, the presence of clouds contributes to the higher persistence in the troposphere because of the capacity of cloud water to accumulate and transport non-volatile (e.g. 2,4-D) and surface-active chemicals (e.g. PFOA). This limits the efficiency of wet deposition from the troposphere enhancing long-range transport.

  1. Mass Spectrometry of Large, Fragile, and Involatile Molecules.

    ERIC Educational Resources Information Center

    Busch, Kenneth L.; Cooks, R. Graham

    1982-01-01

    Desorption ionization (DI) is used to obtain mass spectra of molecules whose vaporization by heating may lead to thermal degradation. Discusses DI techniques, characteristics of DI mass spectra, ion production, current applications of DI in mass spectroscopy, developments in DI, and prospects for future evolution of new DI techniques. (Author/JN)

  2. Electron Impact Ionization of C_2F_6

    NASA Astrophysics Data System (ADS)

    Iga, Ione; Pereira Sanches, Ivana; Srivastava, Santosh Kumar

    2001-10-01

    Besides CF_4, perfluoroethane, C_2F_6, is also one of the fluorocarbon compounds most frequently used in plasma processing applications. Consequently, the knowledge of the ionization properties of C_2F6 is clearly of interest in order to model the plasma-chemical reactions. Nevertheless, only few partial ionization-cross-section measurements [1,2] for this molecule were reported in the literature. Also, the energy range covered in these studies was very limited (below 120 eV). Recently, we have studied these properties. More specifically, partial ionization cross sections (PICS) for the fragments: C^+, F^+, CF^+, CF_2^+, CF_3^+ and C_2F_5^+, produced by electron impact on C_2F_6, were measured in a single-collision condition from near ionization threshold to 1000 eV. In addition, total ionization cross sections (TICS) are also obtained by summing up the PICS's. The comparison of our measured PICS and derived TICS with available data [1-4] will be presented during the Conference. [1] H. U. Poll, J. Meischner, Contrib. Plasma Phys. 27 (1987) 359. [2] C. Q. Jiao, A Garscadden, P. D. Haaland, Chem. Phys. Lett. 310 (1999) 52. [3] H. Nishimura, W. M. Huo, M. A Ali and Y -K. Kim, J. Chem. Phys. 110 (1999) 3811. [4] L. G. Christophorou and J. K. Olthoff, J. Phys. Chem. Ref. Data 27 (1998) 1 and references therein.

  3. High pressure xenon ionization detector

    DOEpatents

    Markey, J.K.

    1989-11-14

    A method is provided for detecting ionization comprising allowing particles that cause ionization to contact high pressure xenon maintained at or near its critical point and measuring the amount of ionization. An apparatus is provided for detecting ionization, the apparatus comprising a vessel containing a ionizable medium, the vessel having an inlet to allow high pressure ionizable medium to enter the vessel, a means to permit particles that cause ionization of the medium to enter the vessel, an anode, a cathode, a grid and a plurality of annular field shaping rings, the field shaping rings being electrically isolated from one another, the anode, cathode, grid and field shaping rings being electrically isolated from one another in order to form an electric field between the cathode and the anode, the electric field originating at the anode and terminating at the cathode, the grid being disposed between the cathode and the anode, the field shaping rings being disposed between the cathode and the grid, the improvement comprising the medium being xenon and the vessel being maintained at a pressure of 50 to 70 atmospheres and a temperature of 0 to 30 C. 2 figs.

  4. High pressure xenon ionization detector

    DOEpatents

    Markey, John K.

    1989-01-01

    A method is provided for detecting ionization comprising allowing particles that cause ionization to contact high pressure xenon maintained at or near its critical point and measuring the amount of ionization. An apparatus is provided for detecting ionization, the apparatus comprising a vessel containing a ionizable medium, the vessel having an inlet to allow high pressure ionizable medium to enter the vessel, a means to permit particles that cause ionization of the medium to enter the vessel, an anode, a cathode, a grid and a plurality of annular field shaping rings, the field shaping rings being electrically isolated from one another, the anode, cathode, grid and field shaping rings being electrically isolated from one another in order to form an electric field between the cathode and the anode, the electric field originating at the anode and terminating at the cathode, the grid being disposed between the cathode and the anode, the field shaping rings being disposed between the cathode and the grid, the improvement comprising the medium being xenon and the vessel being maintained at a pressure of 50 to 70 atmospheres and a temperature of 0.degree. to 30.degree. C.

  5. Measurement of the nuclear polarization of hydrogen and deuterium molecules using a Lamb-shift polarimeter

    SciTech Connect

    Engels, Ralf Gorski, Robert; Grigoryev, Kiril; Mikirtychyants, Maxim; Rathmann, Frank; Seyfarth, Hellmut; Ströher, Hans; Weiss, Philipp; Kochenda, Leonid; Kravtsov, Peter; Trofimov, Viktor; Tschernov, Nikolay; Vasilyev, Alexander; Vznuzdaev, Marat; Schieck, Hans Paetz gen.

    2014-10-15

    Lamb-shift polarimeters are used to measure the nuclear polarization of protons and deuterons at energies of a few keV. In combination with an ionizer, the polarization of hydrogen and deuterium atoms was determined after taking into account the loss of polarization during the ionization process. The present work shows that the nuclear polarization of hydrogen or deuterium molecules can be measured as well, by ionizing the molecules and injecting the H{sub 2}{sup +} (or D{sub 2}{sup +}) ions into the Lamb-shift polarimeter.

  6. Molecular Data for a Biochemical Model of DNA Radiation Damage: Electron Impact Ionization and Dissociative Ionization of DNA Bases and Sugar-Phosphate Backbone

    NASA Technical Reports Server (NTRS)

    Dateo, Christopher E.; Fletcher, Graham D.

    2004-01-01

    As part of the database for building up a biochemical model of DNA radiation damage, electron impact ionization cross sections of sugar-phosphate backbone and DNA bases have been calculated using the improved binary-encounter dipole (iBED) model. It is found that the total ionization cross sections of C3'- and C5'-deoxyribose-phospate, two conformers of the sugar-phosphate backbone, are close to each other. Furthermore, the sum of the ionization cross sections of the separate deoxyribose and phosphate fragments is in close agreement with the C3'- and C5'-deoxyribose-phospate cross sections, differing by less than 10%. Of the four DNA bases, the ionization cross section of guanine is the largest, then in decreasing order, adenine, thymine, and cytosine. The order is in accordance with the known propensity of oxidation of the bases by ionizing radiation. Dissociative ionization (DI), a process that both ionizes and dissociates a molecule, is investigated for cytosine. The DI cross section for the formation of H and (cytosine-Hl)(+), with the cytosine ion losing H at the 1 position, is also reported. The threshold of this process is calculated to be 17.1 eV. Detailed analysis of ionization products such as in DI is important to trace the sequential steps in the biochemical process of DNA damage.

  7. [Development of a membrane inlet-single photon ionization/chemical ionization-mass spectrometer for online analysis of VOCs in water].

    PubMed

    Hua, Lei; Wu, Qing-Hao; Hou, Ke-Yong; Cui, Hua-Peng; Chen, Ping; Zhao, Wu-Duo; Xie, Yuan-Yuan; Li, Hai-Yang

    2011-12-01

    A home-made membrane inlet- single photon ionization/chemical ionization- time-of-flight mass spectrometer has been described. A vacuum ultraviolet (VUV) lamp with photon energy of 10.6 eV was used as the light source for single photon ionization (SPI). Chemical ionization (CI) was achieved through ion-molecule reactions with O2- reactant ions generated by photoelectron ionization. The two ionization modes could be rapidly switched by adjusting electric field in the ionization region within 2 s. Membrane inlet system used for rapid enrichment of volatile organic compounds (VOCs) in water was constructed by using a polydimethylsiloxane (PDMS) membrane with a thickness of 50 microm. A purge gas was added to accelerate desorption of analytes from the membrane surface. The purge gas could also help to prevent the pump oil back-streaming into the ionization region from the analyzer chamber and improve the signal to noise ratio (S/N). Achieved detection limits were 2 microg x L(-1) for methyl tert-butyl ether (MTBE) in SPI mode and 1 microg x L(-1) for chloroform in SPI-CI mode within 10 s analysis time, respectively. The instrument has been successfully applied to the rapid analysis of MTBE in simulated underground water nearby petrol station and VOCs in disinfected drinking water. The results indicate that the instrument has a great application prospect for online analysis of VOCs in water.

  8. Iron ionization and recombination rates and ionization equilibrium

    NASA Technical Reports Server (NTRS)

    Arnaud, M.; Raymond, J.

    1992-01-01

    In the past few years important progress has been made on the knowledge of ionization and recombination rates of iron, an astrophysically abundant heavy element and a major impurity in laboratory fusion devices. We make a critical review of the existing data on ionization and dielectronic recombination and present new computations of radiative recombination rate coefficients of Fe(+14) through Fe(+25) using the photoionization cross sections of Clark et al. (1986). We provide analytical fits to the recommended data (direct ionization and excitation-autoionization cross sections; radiative and dielectronic recombination rate coefficients). Finally we determine the iron ionic fractions at ionization equilibrium and compare them with previous computations as well as with observational data.

  9. Pulsed helium ionization detection system

    DOEpatents

    Ramsey, Roswitha S.; Todd, Richard A.

    1987-01-01

    A helium ionization detection system is provided which produces stable operation of a conventional helium ionization detector while providing improved sensitivity and linearity. Stability is improved by applying pulsed dc supply voltage across the ionization detector, thereby modifying the sampling of the detectors output current. A unique pulse generator is used to supply pulsed dc to the detector which has variable width and interval adjust features that allows up to 500 V to be applied in pulse widths ranging from about 150 nsec to about dc conditions.

  10. Pulsed helium ionization detection system

    DOEpatents

    Ramsey, R.S.; Todd, R.A.

    1985-04-09

    A helium ionization detection system is provided which produces stable operation of a conventional helium ionization detector while providing improved sensitivity and linearity. Stability is improved by applying pulsed dc supply voltage across the ionization detector, thereby modifying the sampling of the detectors output current. A unique pulse generator is used to supply pulsed dc to the detector which has variable width and interval adjust features that allows up to 500 V to be applied in pulse widths ranging from about 150 nsec to about dc conditions.

  11. Ionizing radiation promotes protozoan reproduction

    SciTech Connect

    Luckey, T.D.

    1986-11-01

    This experiment was performed to determine whether ionizing radiation is essential for maximum growth rate in a ciliated protozoan. When extraneous ionizing radiation was reduced to 0.15 mrad/day, the reproduction rate of Tetrahymena pyriformis was significantly less (P less than 0.01) than it was at near ambient levels, 0.5 or 1.8 mrad/day. Significantly higher growth rates (P less than 0.01) were obtained when chronic radiation was increased. The data suggest that ionizing radiation is essential for optimum reproduction rate in this organism.

  12. Study of air pollutant detectors

    NASA Technical Reports Server (NTRS)

    Gutshall, P. L.; Bowles, C. Q.

    1974-01-01

    The application of field ionization mass spectrometry (FIMS) to the detection of air pollutants was investigated. Current methods are reviewed for measuring contaminants of fixed gases, sulfur compounds, nitrogen oxides, hydrocarbons, and particulates. Two enriching devices: the dimethyl silicone rubber membrane separator, and the selective adsorber of polyethylene foam were studied along with FIMS. It is concluded that the membrane enricher system is not a suitable method for removing air pollutants. However, the FIMS shows promise as a useable system for air pollution detection.

  13. Microwave reflectometer ionization sensor

    NASA Technical Reports Server (NTRS)

    Seals, Joseph; Fordham, Jeffrey A.; Pauley, Robert G.; Simonutti, Mario D.

    1993-01-01

    The development of the Microwave Reflectometer Ionization Sensor (MRIS) Instrument for use on the Aeroassist Flight Experiment (AFE) spacecraft is described. The instrument contract was terminated, due to cancellation of the AFE program, subsequent to testing of an engineering development model. The MRIS, a four-frequency reflectometer, was designed for the detection and location of critical electron density levels in spacecraft reentry plasmas. The instrument would sample the relative magnitude and phase of reflected signals at discrete frequency steps across 4 GHz bandwidths centered at four frequencies: 20, 44, 95, and 140 GHz. The sampled data would be stored for later processing to calculate the distance from the spacecraft surface to the critical electron densities versus time. Four stepped PM CW transmitter receivers were located behind the thermal protection system of the spacecraft with horn antennas radiating and receiving through an insulating tile. Techniques were developed to deal with interference, including multiple reflections and resonance effects, resulting from the antenna configuration and operating environment.

  14. Optical ionization detector

    DOEpatents

    Wuest, C.R.; Lowry, M.E.

    1994-03-29

    An optical ionization detector wherein a beam of light is split so that one arm passes through a fiber optics and the other arm passes through a gas-filled region, and uses interferometry to detect density changes in a gas when charged particles pass through it. The gas-filled region of the detector is subjected to a high electric field and as a charged particle traverses this gas region electrons are freed from the cathode and accelerated so as to generate an electron avalanche which is collected on the anode. The gas density is effected by the electron avalanche formation and if the index or refraction is proportional to the gas density the index will change accordingly. The detector uses this index change by modulating the one arm of the split light beam passing through the gas, with respect to the other arm that is passed through the fiber optic. Upon recombining of the beams, interference fringe changes as a function of the index change indicates the passage of charged particles through the gaseous medium. 3 figures.

  15. Optical ionization detector

    DOEpatents

    Wuest, Craig R.; Lowry, Mark E.

    1994-01-01

    An optical ionization detector wherein a beam of light is split so that one arm passes through a fiber optics and the other arm passes through a gas-filled region, and uses interferometry to detect density changes in a gas when charged particles pass through it. The gas-filled region of the detector is subjected to a high electric field and as a charged particle traverses this gas region electrons are freed from the cathode and accelerated so as to generate an electron avalanche which is collected on the anode. The gas density is effected by the electron avalanche formation and if the index or refraction is proportional to the gas density the index will change accordingly. The detector uses this index change by modulating the one arm of the split light beam passing through the gas, with respect to the other arm that is passed through the fiber optic. Upon recombining of the beams, interference fringe changes as a function of the index change indicates the passage of charged particles through the gaseous medium.

  16. Martian Meteor Ionization Layers

    NASA Technical Reports Server (NTRS)

    Grebowsky, J. M.; Pesnell, W. D.

    1999-01-01

    Small interplanetary grains bombard Mars, like all the solar system planets, and, like all the planets with atmospheres, meteoric ion and atom layers form in the upper atmosphere. We have developed a comprehensive one-dimensional model of the Martian meteoric ionization layer including a full chemical scheme. A persistent layer of magnesium ions should exist around an altitude of 70 km. Unlike the terrestrial case, where the metallic ions are formed via charge-exchange with the ambient ions, Mg(+) in the Martian atmosphere is produced by photoionization. Nevertheless, the predicted metal layer peak densities for Earth and Mars are similar. Diffusion solutions, such as those presented here, should be a good approximation of the metallic ions in regions where the magnetic field is negligible and may provide a significant contribution to the nightside ionosphere. The low ultraviolet absorption of the Martian atmosphere may make Mars an excellent laboratory in which to study meteoric ablation. Resonance lines not seen in the spectra of terrestrial meteors may be visible to a surface observatory in the Martian highlands.

  17. The efficiencies of resonant and nonresonant multiphoton ionization in the femtosecond region.

    PubMed

    Kouno, Hiroaki; Imasaka, Totaro

    2016-09-21

    Ionization efficiency in mass spectrometry was examined for three types of molecules under different ionization schemes, i.e., resonant/nonresonant and two-photon/three-photon ionization, using an ultraviolet (UV) femtosecond laser at different wavelengths, pulse energies, and pulse widths. The efficiency of nonresonant ionization could be improved substantially by decreasing the laser pulse width. The effect of resonance was minimal when an ultrashort optical pulse of less than 100 fs was employed for ionization in the UV region. Three-photon ionization was less efficient than two-photon ionization, but the difference was not significant at shorter pulse widths in the femtosecond region. Although the excess energy can be decreased by optimizing the laser wavelength in the case of nonresonant ionization, fragmentation was not suppressed in the cases studied here. However, fragmentation was drastically suppressed when the laser pulse width was decreased. Thus, this approach of using an ultrashort optical pulse would provide a new tool for soft ionization and then for more reliable identification of an analyte.

  18. Electron impact ionization of CHF2Cl: Unusual ordering of ionization energies for parent and fragment ions

    NASA Astrophysics Data System (ADS)

    Cicman, P.; Gluch, K.; Pelc, A.; Sailer, W.; Matt-Leubner, S.; Scheier, P.; Matejcik, S.; Lukac, P.; Robertson, W. D.; Compton, R. N.; Märk, T. D.

    2003-12-01

    Electron impact ionization of the chlorodifluoromethane molecule is studied using crossed beams of high-resolution electrons and an effusive molecular beam of CHF2Cl. Ionization energies (IEs) for many positive ions from CHF2Cl (CHF2Cl+,CF2Cl+,CHFCl+,CFCl+,CHF2+,CF2+,HCl+,Cl+,CF+,CH+,F+ C+) are determined from a careful examination of the threshold behavior of the ionization cross sections. Reaction pathways for the dissociative ionization products are suggested using known thermodynamic quantities. Surprisingly, it is observed that the ionization threshold for the parent positive ion IE(CHF2Cl+/CHF2Cl)=12.50(±0.05) eV lies above that for the fragment ions CHF2+, CHFCl+, and CF+ [IE(CHF2+/CHF2Cl)=12.24(±0.03) eV, IE(CHFCl+/CHF2Cl)=12.3(±0.05) eV, and IE(CF+/CHF2Cl)=11.5(±0.1) eV]. Experiments using a three sector field BEE mass spectrometer provide evidence for the existence of two states of the parent CHF2Cl+ ion, one exhibiting a short lifetime of about 2 μs and another parent ion state which appears to be stable on the time scale of the experiment (>20 μs) with an IE of 12.50 eV.

  19. Extracting amplitudes for single and double ionization from a time-dependent wave packet

    SciTech Connect

    Palacios, A.; Rescigno, T. N.; McCurdy, C. W.

    2007-10-15

    A method is described for extracting double ionization amplitudes from a quantum wave packet for an atom after a short radiation pulse, but while the electrons are still interacting. The procedure involves the use of exterior complex scaling to effectively propagate the field-free solution to infinite times, and allows the use of existing integral formulas for double ionization amplitudes for two electron atoms and molecules.

  20. Ionization-based detectors for gas chromatography.

    PubMed

    Poole, Colin F

    2015-11-20

    The gas phase ionization detectors are the most widely used detectors for gas chromatography. The column and makeup gases commonly used in gas chromatography are near perfect insulators. This facilitates the detection of a minute number of charge carriers facilitating the use of ionization mechanisms of low efficiency while providing high sensitivity. The main ionization mechanism discussed in this report are combustion in a hydrogen diffusion flame (flame ionization detector), surface ionization in a plasma (thermionic ionization detector), photon ionization (photoionization detector and pulsed discharge helium ionization detector), attachment of thermal electrons (electron-capture detector), and ionization by collision with metastable helium species (helium ionization detector). The design, response characteristics, response mechanism, and suitability for fast gas chromatography are the main features summarized in this report. Mass spectrometric detection and atomic emission detection, which could be considered as ionization detectors of a more sophisticated and complex design, are not discussed in this report. PMID:25757823