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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

    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.

  3. 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.

  4. 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.

  5. 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.

  6. Strong-field ionization of a heteronuclear diatomic molecule

    SciTech Connect

    Ren, Xianghe; Nakajima, Takashi

    2010-12-15

    We theoretically study strong-field ionization of a heteronuclear diatomic molecule, CO, by calculating the photoelectron angular distributions (PADs) and the total ionization rates using linearly and circularly polarized laser fields. We find that, although the PADs of CO generally do not have inversion symmetry, they become more inversion symmetric as the photoelectron energy increases. Heteronuclear features of CO upon ionization are better understood by comparing the results with those of a representative of homonuclear molecules, N{sub 2}, in that, although there are some similarities between CO and N{sub 2} due to the same orbital symmetry, {sigma}{sub g}, there are some differences between them in terms of the ionization suppression and orientation dependence of the total ionization yield. Namely, CO behaves more like an atom in the low-intensity range in a sense that ionization takes place mainly from the neighborhood of the C core, while it behaves more like a double-core molecule in the high-intensity range since ionization takes place from the neighborhood of both C and O cores. This explains why ionization suppression of CO is not seen at the low intensity but it becomes more visible at the high intensity range.

  7. 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

  8. Ionization of the glycerin molecule by the electron impact

    NASA Astrophysics Data System (ADS)

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

    2014-10-01

    The paper describes experimental method for and presents the results of studying positive ion yields produced due to direct and dissociative electron-impact ionization of the glycerin molecule. The mass spectra of the glycerin molecule are studied in the range of mass numbers of 10-95 amu at different temperatures. The energy dependences of the ionization efficiency cross sections of the glycerin molecule ions produced by a monoenergetic electron beam are analyzed; using these dependences, the appearance energies of fragment ions are determined. The dynamics of fragment ion formation is investigated in the temperature range of 300-340 K.

  9. 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).

  10. 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

  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. Coherent Dynamics Following Strong Field Ionization of Polyatomic Molecules

    NASA Astrophysics Data System (ADS)

    Konar, Arkaprabha; Shu, Yinan; Lozovoy, Vadim; Jackson, James; Levine, Benjamin; Dantus, Marcos

    2015-03-01

    Molecules, as opposed to atoms, present confounding possibilities of nuclear and electronic motion upon strong field ionization. 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. We consider here 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 delay scans show that among positional isomers the variations in relative energies, amounting to only a few hundred meVs, influence the dynamical behavior of the molecules despite their having experienced such high fields (V/Å). Ab initio calculations were performed to predict dynamics along with single and multiphoton resonances in the neutral and ionic states. We propose that single electron ionization occurs within an optical cycle with the electron carrying away essentially all of the energy, leaving behind little internal energy in the cation. Evidence for this observation comes from coherent vibrational motion governed by the potential energy surface of the ground state of the cation. Subsequent fragmentation of the cation takes place as a result of further photon absorption modulated by one- and two-photon resonances, which provide sufficient energy to overcome the dissociation energy.

  13. 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.

  14. Anti-Stokes-enhanced tunneling ionization of molecules

    NASA Astrophysics Data System (ADS)

    Kornev, Aleksei S.; Zon, Boris A.

    2012-10-01

    We consider the influence of vibrational motion of nuclei on the tunneling ionization of a molecule in a strong light field. Unlike the molecular Ammosov-Delone-Krainov (MO-ADK) model [X. M. Tong , Phys. Rev. APLRAAN1050-294710.1103/PhysRevA.66.033402 66, 033402 (2002)], the Franck-Condon factors that take into consideration the quantization of nuclear vibrations are introduced in the theory. Modification of the vibrational motion of nuclei by the external field leads to the time-dependent constant in the asymptotic form of the electronic wave function. This in turn leads to a more significant modification of the Keldysh theory for the tunnel effect in molecules as compared to the MO-ADK model. We take into account the possibility of vibrational quantum numbers changing in a neutral molecule and in a molecular ion in the process of the tunneling ionization, which in principle enables one to get molecular ions of a certain isotopic composition if the vibrational states of the neutral molecules with this isotopic composition are pumped before ionization. We present numerical results illustrating this possibility for the isotopes of a hydrogen molecule.

  15. 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.

  16. 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.

  17. Molecular surface analysis by laser ionization of desorbed molecules

    SciTech Connect

    Pellin, M.J.; Lykke, K.R.; Wurz, P.; Parker, D.H.

    1992-01-01

    While elemental analysis of surfaces has progressed dramatically over the past ten years, quantitative molecular surface analysis remains difficult. This is particularly true in the analysis of complex materials such as polymers and rubbers which contain a wide compliment of additives and pigments to enhance their material characteristics. For mass spectrometric analysis the difficulty is two fold. First, desorption of surface molecules must be accompanied with minimal fragmentation and collateral surface damage. Second, the desorbed molecules must be ionized for subsequent mass analysis with high efficiency and without significant cracking. This paper focuses on the second of these problems.

  18. Molecular surface analysis by laser ionization of desorbed molecules

    SciTech Connect

    Pellin, M.J.; Lykke, K.R.; Wurz, P.; Parker, D.H.

    1992-07-01

    While elemental analysis of surfaces has progressed dramatically over the past ten years, quantitative molecular surface analysis remains difficult. This is particularly true in the analysis of complex materials such as polymers and rubbers which contain a wide compliment of additives and pigments to enhance their material characteristics. For mass spectrometric analysis the difficulty is two fold. First, desorption of surface molecules must be accompanied with minimal fragmentation and collateral surface damage. Second, the desorbed molecules must be ionized for subsequent mass analysis with high efficiency and without significant cracking. This paper focuses on the second of these problems.

  19. 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.

  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. 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.

  2. Dissociative ionization of sodium molecules via repulsive Rydberg states

    NASA Astrophysics Data System (ADS)

    Chen, Hong

    In this thesis, an investigation of two color resonance multiphoton ionization (REMPI) and fragmentation processes in Na2 has been performed in combination with Linear Time-of-Flight Mass Spectrometry technique. The ionization and dissociative ionizations channels in the energy range up to 2500cm -1 above the dissociative ionization threshold into Na(3s)+Na ++e have been studied. After a mild supersonic expansion from the beam source, neutral sodium dimers in the ground state have been produced. Two tunable, pulsed lasers excite Na2 molecules via the intermediate A1S+u state to a single ro-vibrational level of the second intermediate 21pig state. Following absorption of a third photon, the total energy is above the dissociation limit into Na(3s) + Na+ + e. Typically, a small portion of atomic ions is produced under our experimental conditions. By varying the total available energy below and through the doubly excited states correlating with the Na(3p)+Na(4s) atom pair, there is no evidence that the doubly excited states positioned in the ionic continuum get involved. By calculation of the expected transition probabilities for all possible channels which can decay directly and indirectly into atomic ions, I find that direct dissociative ionization via 12S+u is impossible. The transition probabilities for dissociative ionization via the repulsive Rydberg states with principal quantum numbers n from 5˜12 converging toward the 12S+u state are three to four orders of magnitude larger than those for direct ionization into the continuum of the X2S+g ground state. These repulsive Rydberg states are much more likely to play a role in the photo-ionization through the intermediate 21Pg state. A semi-classical model which was originally developed for negative ion dissociative attachment (O'MAL'67) describes how dissociative ionization occurs along the repulsive Rydberg states. Its prediction concerning the ratio of atomic to molecular ion production as a function of initial

  3. Small molecule ambient mass spectrometry imaging by infrared laser ablation metastable-induced chemical ionization.

    PubMed

    Galhena, Asiri S; Harris, Glenn A; Nyadong, Leonard; Murray, Kermit K; Fernández, Facundo M

    2010-03-15

    Presented here is a novel ambient ion source termed infrared laser ablation metastable-induced chemical ionization (IR-LAMICI). IR-LAMICI integrates IR laser ablation and direct analysis in real time (DART)-type metastable-induced chemical ionization for open air mass spectrometry (MS) ionization. The ion generation in the IR-LAMICI source is a two step process. First, IR laser pulses impinge the sample surface ablating surface material. Second, a portion of ablated material reacts with the metastable reactive plume facilitating gas-phase chemical ionization of analyte molecules generating protonated or deprotonated species in positive and negative ion modes, respectively. The successful coupling of IR-laser ablation with metastable-induced chemical ionization resulted in an ambient plasma-based spatially resolved small molecule imaging platform for mass spectrometry (MS). The analytical capabilities of IR-LAMICI are explored by imaging pharmaceutical tablets, screening counterfeit drugs, and probing algal tissue surfaces for natural products. The resolution of a chemical image is determined by the crater size produced with each laser pulse but not by the size of the metastable gas jet. The detection limits for an active pharmaceutical ingredient (acetaminophen) using the IR-LAMICI source is calculated to be low picograms. Furthermore, three-dimensional computational fluid dynamic simulations showed improvements in the IR-LAMICI ion source are possible. PMID:20155978

  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. Revisiting molecular ionization: Does a molecule like to share?

    NASA Astrophysics Data System (ADS)

    Madsen, C. B.; Esry, B. D.

    2012-06-01

    The ever-increasing detail obtained in strong-field experiments calls for a deeper understanding of the laser-molecule interaction. For instance, recent measurements reported in PRL 107, 143004 (2011) reveal a limitation in understanding strong-field ionization dynamics in terms of the strong-field approximation. We have addressed the question of how the electron and the nuclei share the energy when H2^+ breaks up in the presence of an intense IR field via the process: H2^++nφ->p+p+e^-. Solving the time-dependent Schr"odinger equation and calculating the ionization probability resolved as a function of the asymptotic electron energy and the nuclear kinetic energy release (KER) allow us to give an answer. The energy sharing is non-trivial and plays an important role in the prediction of, for instance, the KER. We also address the limitations of current understanding of molecular ionization by comparing to models like the strong-field approximation and the Floquet picture. Such benchmarking may be facilitated by XUV+IR pump-probe schemes and carrier-envelope-phase control that allow for time-resolved and spatial probing of the dynamics.

  6. Single ionization of water molecules in collisions with bare ions

    NASA Astrophysics Data System (ADS)

    Mondal, A.; Mandal, C. R.; Purkait, M.

    2016-04-01

    We present the double differential cross sections (DDCSs) for the direct ionization of water molecules by impact of fully stripped helium, carbon and oxygen atoms, respectively. In the present formalism, we have represented the wavefunction in the entrance channel as the product of a plane wave for the projectile and an accurate one-center-molecular wavefunction of the water molecule by Moccia (1964 J. Chem. Phys. 40 2186). In the exit channel, we have expressed the total wavefunction as the product of pair-wise Coulomb wavefunctions among the ejected electron, projectile ion and the residual target ion, respectively. The contributions of DDCSs for five different molecular orbitals of water to the spectrum of angular distributions have been analyzed for several electron emission energies. The present results for DDCSs are compared with existing experimental and theoretical findings. We find an overall good agreement between our calculated results and the experimental findings for electron emission cross sections. In addition, DDCS results for ionization from different orbitals at a few electron emission energies are given in tabular form.

  7. 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.

  8. Electron ionization and ion-molecule reactions of triethylborane

    NASA Astrophysics Data System (ADS)

    Jiao, Charles; Adams, Steven

    2015-09-01

    Triethylborane (TEB) is used as a radical initiator in many chemical reactions and as an excellent ignition source for jet engines and rocket engines. In this paper we will report our recent study on the ion chemistries of TEB relevant to the charged particle processes in plasmas involving TEB. The total cross section of electron ionization of TEB is found to have a maximum of 2.2×10-15 cm2 at 75 +10 eV electron energy. Product ions from the ionization include C2H2-5+, BCH4+, BC2, 4,6+, BC3H4, 6+, BC4H8, 10+ and BC6H15+, among which BC6H15+, BC4H10+ and BC2H6+ are the most abundant ions. These ions react with TEB via various mechanisms including charge-transfer, alkyde-transfer and association reaction. The common and major product ions from the ion-molecule reactions are BC4H10+ and BC2H6+, formed by simple ethide-transfer and ethide-transfer followed by dissociation (loss of C2H4) , respectively.

  9. Intense field ionization of diatomic molecules: Two-center interference and tunneling

    SciTech Connect

    Chen, Y. J.; Hu Bambi

    2010-01-15

    We investigate the ionization of model diatomic molecules exposed in intense laser fields both numerically and analytically. Our simulations show that, in the tunneling region, the interplay of the tunneling effect and molecular two-center structure has an important role in ionization. It can lead to the enhancement of ionization in molecules as compared to their reference atoms with similar ionization potential. Furthermore, it also plays a dominating role in the angle dependence of molecular ionization. This effect is different from that of two-center interference in ionization. The latter manifests itself remarkably in the multiphoton region and can cause the ionization suppression of molecules in this region. Our further comparisons suggest the significant influence of the orbital symmetry of the reference atom on molecular ionization comparison experiments.

  10. Atmospheric Ionizing Radiation (AIR) ER-2 Preflight Analysis

    NASA Technical Reports Server (NTRS)

    Tai, Hsiang; Wilson, John W.; Maiden, D. L.

    1998-01-01

    Atmospheric ionizing radiation (AIR) produces chemically active radicals in biological tissues that alter the cell function or result in cell death. The AIR ER-2 flight measurements will enable scientists to study the radiation risk associated with the high-altitude operation of a commercial supersonic transport. The ER-2 radiation measurement flights will follow predetermined, carefully chosen courses to provide an appropriate database matrix which will enable the evaluation of predictive modeling techniques. Explicit scientific results such as dose rate, dose equivalent rate, magnetic cutoff, neutron flux, and air ionization rate associated with those flights are predicted by using the AIR model. Through these flight experiments, we will further increase our knowledge and understanding of the AIR environment and our ability to assess the risk from the associated hazard.

  11. Ionizing radiation induces human intercellular adhesion molecule-1 in vitro.

    PubMed

    Behrends, U; Peter, R U; Hintermeier-Knabe, R; Eissner, G; Holler, E; Bornkamm, G W; Caughman, S W; Degitz, K

    1994-11-01

    Intercellular adhesion molecule-1 (ICAM-1) plays a central role in various inflammatory reactions and its expression is readily induced by inflammatory stimuli such as cytokines or ultraviolet irradiation. We have investigated the effect of ionizing radiation (IR) on human ICAM-1 expression in human cell lines and skin cultures. ICAM-1 mRNA levels in HL60, HaCaT, and HeLa cells were elevated at 3-6 h after irradiation and increased with doses from 10-40 Gy. The rapid induction of ICAM-1 occurred at the level of transcription, was independent of de novo protein synthesis, and did not involve autocrine stimuli including tumor necrosis factor-alpha and interleukin-1. IR also induced ICAM-1 cell surface expression within 24 h. Immunohistologic analysis of cultured human split skin revealed ICAM-1 upregulation on epidermal keratinocytes and dermal microvascular endothelial cells 24 h after exposure to 6 Gy. In conclusion, we propose ICAM-1 as an important radiation-induced enhancer of immunologic cell adhesion, which contributes to inflammatory reactions after local and total body irradiation. PMID:7963663

  12. The formation of molecules in interstellar clouds from singly and multiply ionized atoms

    NASA Technical Reports Server (NTRS)

    Langer, W. D.

    1978-01-01

    The suggestion is considered that multiply ionized atoms produced by K- and L-shell X-ray ionization and cosmic-ray ionization can undergo ion-molecule reactions and also initiate molecule production. The role of X-rays in molecule production in general is discussed, and the contribution to molecule production of the C(+) radiative association with hydrogen is examined. Such gas-phase reactions of singly and multiply ionized atoms are used to calculate molecular abundances of carbon-, nitrogen-, and oxygen-bearing species. The column densities of the molecules are evaluated on the basis of a modified version of previously developed isobaric cloud models. It is found that reactions of multiply ionized carbon with H2 can contribute a significant fraction of the observed CH in diffuse interstellar clouds in the presence of diffuse X-ray structures or discrete X-ray sources and that substantial amounts of CH(+) can be produced under certain conditions.

  13. 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.

  14. Electron ionization of open/closed chain isocarbonic molecules relevant in plasma processing: Theoretical cross sections

    SciTech Connect

    Patel, Umang R.; Joshipura, K. N.; Pandya, Siddharth H.; Kothari, Harshit N.

    2014-01-28

    In this paper, we report theoretical electron impact ionization cross sections from threshold to 2000 eV for isocarbonic open chain molecules C{sub 4}H{sub 6}, C{sub 4}H{sub 8}, C{sub 4}F{sub 6} including their isomers, and closed chain molecules c-C{sub 4}H{sub 8} and c-C{sub 4}F{sub 8}. Theoretical formalism employed presently, viz., Complex Scattering Potential-ionization contribution method has been used successfully for a variety of polyatomic molecules. The present ionization calculations are very important since results available for the studied targets are either scarce or none. Our work affords comparison of C{sub 4} containing hydrocarbon versus fluorocarbon molecules. Comparisons of the present ionization cross sections are made wherever possible, and new ionization data are also presented.

  15. Ionization of organic molecules with ultraviolet lasers: A technique for generating large, well-defined ionized volumes

    NASA Astrophysics Data System (ADS)

    Woodworth, J. R.; Green, T. A.; Frost, C. A.

    1985-03-01

    In this paper we report a technique for generating a large, homogeneous volume of ionized gas and for making time-resolved measurements of its electron density. We also report absolute photoionization coefficients for a number of molecules. These coefficients will allow calculation of peak electron densities obtained in other ionization-related experiments. In our technique, the beam from a rare-gas halogen laser photoionizes organic molecules that have been seeded into a buffer gas. Ionization is accomplished by the absorption of two photons. We have analyzed the electron densities produced by photoionization with a microwave interferometer that measures the electron density in the ionized gas with a time-resolution of a few nanoseconds. Some of the organic molecules photoionized in this work produce electron-ion pairs with an efficiency more than five orders of magnitude higher than commonly used laboratory ionization sources such as ArF laser photoionization of NO. We have also studied the effect of attaching gases on the ionized mixtures and have demonstrated that addition of as little as 10 Torr of SF6 can reduce the peak electron density observed by a factor of 103.

  16. Application of the partial-Fourier-transform approach for tunnel ionization of molecules

    NASA Astrophysics Data System (ADS)

    Liu, Mingming; Liu, Yunquan

    2016-04-01

    Combining the partial-Fourier-transform approach with Wenzel-Kramers-Brillouin approximation, we theoretically study the strong-field tunneling ionization of diatomic and polyatomic molecules. First we obtain the analytical expression of momentum distribution at the tunnel exit of diatomic molecules, and then we calculate the alignment-dependent ionization rate at different laser intensities and internuclear distances. We show that the internuclear distance has a significant effect on the alignment dependence of the ionization rate. Using this approach, we can also separate the contributions of each atomic center and show the interference effect between them. Finally, we extend this method to a polyatomic molecule, benzene, as an example.

  17. Developing of a New Atmospheric Ionizing Radiation (AIR) Model

    NASA Technical Reports Server (NTRS)

    Clem, John M.; deAngelis, Giovanni; Goldhagen, Paul; Wilson, John W.

    2003-01-01

    As a result of the research leading to the 1998 AIR workshop and the subsequent analysis, the neutron issues posed by Foelsche et al. and further analyzed by Hajnal have been adequately resolved. We are now engaged in developing a new atmospheric ionizing radiation (AIR) model for use in epidemiological studies and air transportation safety assessment. A team was formed to examine a promising code using the basic FLUKA software but with modifications to allow multiple charged ion breakup effects. A limited dataset of the ER-2 measurements and other cosmic ray data will be used to evaluate the use of this code.

  18. 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.

  19. Ionization suppression of Cl{sub 2} molecules in intense laser fields

    SciTech Connect

    Benis, E.P.; Xia, J.F.; Tong, X.M.; Faheem, M.; Zamkov, M.; Shan, B.; Richard, P.; Chang, Z.

    2004-08-01

    The strong field ionization of Cl{sub 2} molecules is investigated by using an ultrashort pulse Ti:sapphire laser. A spatial imaging technique is used in such measurements to reduce the effect of spatial integration. Cl{sub 2} shows strong ionization suppression as do other diatomic molecules having valence orbitals with antibonding symmetry (O{sub 2},S{sub 2}) when compared with the field ionization of atoms with nearly identical ionization potential. A more general molecular tunneling ionization model is proposed, and the calculations are in reasonable agreement with the measurements. Our results support that antibonding leads to ionization suppression, a trend that only F{sub 2} goes against and that needs to be further investigated.

  20. First-principles calculations for the tunnel ionization rate of atoms and molecules

    SciTech Connect

    Otobe, T.; Yabana, K.; Iwata, J.-I.

    2004-05-01

    We present first-principles calculations for the tunnel ionization rate of some atoms and molecules in a static intense electric field. The Gamow state is calculated to describe the ionization process in the Kohn-Sham formalism with the self-interaction correction. The tunnel ionization rate is obtained from the imaginary part of the Gamow state eigenvalue. The ionization rates of rare-gas atoms Ar and Xe and diatomic molecules N{sub 2}, O{sub 2}, and F{sub 2} are investigated. The calculations describe well the observed behavior of the tunnel ionization. The results also show good correspondence with the Ammosov-Delone-Krainov model for rare-gas atoms. We find that the properties of the highest occupied orbital have significant effects on the ionization rate. In particular, our calculation reproduces the suppression of the ionization rate of O{sub 2} molecule in comparison with that of Xe atom. We also find that the ionization rates of O{sub 2} and F{sub 2} molecules are very sensitive to the relative angle between the electric field and the molecular axis, reflecting properties of the highest occupied orbital.

  1. 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.

  2. 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

  3. 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.

  4. 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.

  5. 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.

  6. 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.

  7. Corona discharge ionization of paracetamol molecule: Peak assignment

    NASA Astrophysics Data System (ADS)

    Bahrami, H.; Farrokhpour, H.

    2015-01-01

    Ionization of paracetamol was investigated using ion mobility spectrometry equipped with a corona discharge ionization source. The measurements were performed in the positive ion mode and three peaks were observed in the ion mobility spectrum. Experimental evidence and theoretical calculations were used to correlate the peaks to related ionic species of paracetamol. Two peaks were attributed to protonated isomers of paracetamol and the other peak was attributed to paracetamol fragment ions formed by dissociation of the N-C bond after protonation of the nitrogen atom. It was observed that three sites of paracetamol compete for protonation and their relative intensities, depending on the sample concentration. The ratio of ion products could be predicted from the internal proton affinity of the protonation sites at each concentration.

  8. Corona discharge ionization of paracetamol molecule: peak assignment.

    PubMed

    Bahrami, H; Farrokhpour, H

    2015-01-25

    Ionization of paracetamol was investigated using ion mobility spectrometry equipped with a corona discharge ionization source. The measurements were performed in the positive ion mode and three peaks were observed in the ion mobility spectrum. Experimental evidence and theoretical calculations were used to correlate the peaks to related ionic species of paracetamol. Two peaks were attributed to protonated isomers of paracetamol and the other peak was attributed to paracetamol fragment ions formed by dissociation of the N-C bond after protonation of the nitrogen atom. It was observed that three sites of paracetamol compete for protonation and their relative intensities, depending on the sample concentration. The ratio of ion products could be predicted from the internal proton affinity of the protonation sites at each concentration. PMID:25128677

  9. 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.

  10. Interference in above-threshold-ionization electron distributions from molecules

    SciTech Connect

    Henkel, Jost; Lein, Manfred; Engel, Volker

    2011-05-15

    We present quantum-mechanical studies on above-threshold ionization of molecular ions in two and three dimensions. The momentum distributions show signatures of interfering emissions from the molecular centers. These structures deviate from a simple double-slit model that ignores the electron-ion interaction, but they are reproduced by an eikonal model. Such distortions of the interference pattern are partly responsible for the absence of clear interference patterns in the angle-integrated electron energy spectra.

  11. 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.

  12. 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)

  13. 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)

  14. 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.

  15. Single electron impact ionization of the methane molecule

    NASA Astrophysics Data System (ADS)

    Bouamoud, Mammar; Sahlaoui, Mohammed; Benmansour, Nour El Houda; Atomic and Molecular Collisions Team

    2014-10-01

    Triply differential cross sections (TDCS) results of electron-impact ionization of the inner 2a1 molecular orbital of CH4 are presented in the framework of the Second Born Approximation and compared with the experimental data performed in coplanar asymmetric geometry. The cross sections are averaged on the random orientations of the molecular target for accurate comparison with experiments and are compared also with the theoretical calculations of the Three Coulomb wave (3CW) model. Our results are in good agreement with experiments and 3CW results in the binary peak. In contrast the Second Born Approximation yields a significant higher values compared to the 3CW results for the recoil peak and seems to describe suitably the recoil region where higher order effects can occur with the participation of the recoiling ion in the collision process.

  16. High-order harmonic cutoff extension of the O{sub 2} molecule due to ionization suppression

    SciTech Connect

    Shan Bing; Tong Xiaomin; Zhao Zengxiu; Chang Zenghu; Lin, C.D.

    2002-12-01

    High-order harmonic generation has been observed experimentally from O{sub 2} molecules at the saturation ionization intensity. The harmonic cutoff extends far beyond the cutoff of Xe despite both have nearly equal ionization potentials. In contrast, the harmonic spectra for N{sub 2} and Ar, which have almost the same ionization potentials, are essentially close to each other. We show the extension of harmonic cutoff in O{sub 2} is a consequence of ionization suppression. Using a simple modified tunneling ionization model for molecules, we predict both the harmonic cutoff extension and the ionization suppression semiquantitatively.

  17. Ion appearance energies at electron-impact dissociative ionization of sulfur hexafluoride molecule and its fragments

    NASA Astrophysics Data System (ADS)

    Demesh, Shandor Sh.; Remeta, Eugene Yu.

    2015-07-01

    Theoretical analysis of appearance energies for SF{/k +} ( k = 0- n) ion fragments of SF6 molecule as well as F+ and F{2/+} ions at electron-impact dissociative ionization of SF n ( n = 1-6) molecules is presented. Theoretical methods of GAMESS software package were used to calculate the total energies of neutral and charged molecular and atomic fragments. The dissociative ionization process is concluded to occur via repulsive highly-excited electronic states of the SF6 molecule and its fragments, due to which the observed appearance energies exceed the theoretical values. The electron binding energies on the molecular orbitals in the SF6 molecule are compared with the ion fragment appearance energies.

  18. Accuracy of Theoretical Calculations for Electron-Impact Ionization of atoms and Molecules

    NASA Astrophysics Data System (ADS)

    Madison, Don

    2015-09-01

    In the last two decades, there have been several close-coupling approaches developed which can accurately calculate the triply differential cross sections for electron impact ionization of effective one and two electron atoms. The agreement between experiment and theory is not particularly good for more complicated atoms and molecules. Very recently, a B-spline R-matrix with pseudostates (BSRPS) approach was used to investigate low energy electron impact ionization of neon and very good agreement with experiment was found. The perturbative 3-body distorted wave (3DW) approach which includes the exact final state electron-electron interaction (post collision interaction - PCI) gave comparably good agreement with experiment. For ionization of molecules, there have been numerous studies of high-energy electron impact. These studies are called EMS (Electron Momentum Spectroscopy) and they were very valuable in determining the accuracy of molecular wavefunctions since the measured cross sections were proportional to the momentum space molecular wavefunction. More recently, lower energy collisions have started to be measured and these cross sections are much more difficult for theory since the detailed kinematics of the experiment become important. So far, the only close coupling calculation reported for ionization of molecules is the time-dependent close-coupling calculation (TDCC) which has been developed for ionization of H2 and it yields relative good agreement with experiment. Again the molecular 3-body distorted wave (M3DW) gave equally good agreement with experiment. For polyatomic molecules, the only theory available is the M3DW. In this talk, I will show the current status of agreement between experiment and theory for low and intermediate energy single ionization of atoms and molecules. Work supported by the NSF and XSEDE.

  19. 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

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

    DOE PAGESBeta

    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.

  1. Properties of hollow molecules probed by single-photon double ionization.

    PubMed

    Lablanquie, P; Penent, F; Palaudoux, J; Andric, L; Selles, P; Carniato, S; Bučar, 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(2)(2+) K(-2) main and satellite states and the strong chemical shifts of double K holes on an oxygen atom in CO, CO2, and O2 molecules. PMID:21405466

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

    NASA Astrophysics Data System (ADS)

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

    2011-02-01

    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 N22+ K-2 main and satellite states and the strong chemical shifts of double K holes on an oxygen atom in CO, CO2, and O2 molecules.

  3. 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.

  4. 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.

  5. Immunomodulation of classical and non-classical HLA molecules by ionizing radiation.

    PubMed

    Gallegos, Cristina E; Michelin, Severino; Dubner, Diana; Carosella, Edgardo D

    2016-05-01

    Radiotherapy has been employed for the treatment of oncological patients for nearly a century, and together with surgery and chemotherapy, radiation oncology constitutes one of the three pillars of cancer therapy. Ionizing radiation has complex effects on neoplastic cells and on tumor microenvironment: beyond its action as a direct cytotoxic agent, tumor irradiation triggers a series of alterations in tumoral cells, which includes the de novo synthesis of particular proteins and the up/down-regulation of cell surface molecules. Additionally, ionizing radiation may induce the release of "danger signals" which may, in turn lead to cellular and molecular responses by the immune system. This immunomodulatory action of ionizing radiation highlights the importance of the combined use (radiotherapy plus immunotherapy) for cancer healing. Major histocompatibility complex antigens (also called Human Leukocyte Antigens, HLA in humans) are one of those molecules whose expression is modulated after irradiation. This review summarizes the modulatory properties of ionizing radiation on the expression of HLA class I (classical and non-classical) and class II molecules, with special emphasis in non-classical HLA-I molecules. PMID:27113815

  6. Multiphoton fragmentation and ionization of CF{sub 2}HCl molecules and clusters by UV radiation

    SciTech Connect

    Lokhman, V. N.; Ogurok, D. D.; Ryabov, E. A.

    2006-07-15

    The results of experimental studies of multiphoton ionization of CF{sub 2}HCl molecules and clusters by UV laser radiation in the wavelength range 217-236 nm are reported. In the case of molecules, the main reaction products are CF{sub 2}H{sup +} and CF{sup +} ions as well as atomic chlorine. It is found that the spectra of the products of ionization of free molecules and molecules condensed into clusters differ qualitatively: multiphoton ionization of clusters does not yield CF{sub 2}H{sup +} ions. The dependences of the ion yield on the intensity of laser radiation and its wavelength are measured. The effect of a constant electric field and the radiation spectral width on the multiphoton ionization process is demonstrated. The shape of the velocity distributions is determined for a number of products. A strong anisotropy is detected in the reaction of formation of CF{sub 2}H{sup +} ions. Possible mechanisms for these processes are discussed.

  7. Molecular isomerization and fragmentation of polyatomic molecules controlled by inner-valence recollision-ionization

    NASA Astrophysics Data System (ADS)

    Xie, X.; Doblhoff-Dier, K.; Roither, S.; Schöffler, M.; Kartashov, D.; Xu, H.; Rathje, T.; Paulus, G. G.; Baltuška, A.; Gräfe, S.; Kitzler, M.

    2014-04-01

    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.

  8. Selective inner-valence ionization of aligned polyatomic molecules for controlling molecular fragmentation

    NASA Astrophysics Data System (ADS)

    Xie, X.; Doblhoff-Dier, K.; Xu, H.; Roither, S.; Iwasaki, A.; Schöffler, M.; Kartashov, D.; Yamanouchi, K.; Baltuška, A.; Gräfe, S.; Kitzler, M.

    2014-04-01

    We show experimentally and theoretically, using acetylene as an example, that the strong preponderance of ionization from specific molecular orbitals to the alignment of the molecular axis with respect to the laser polarization direction allows implementing a method for controlling fragmentation reactions of polyatomic molecules.

  9. 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.

  10. Photoelectron spectroscopic studies of polyatomic molecules: Degree of orientation and ionization of rotationally state selected, oriented molecules

    NASA Astrophysics Data System (ADS)

    Chandra, N.; Chakraborty, M.

    1991-11-01

    In this paper we report theoretical studies of angle-resolved photoelectron spectroscopy (ARPES) and of circular dichroism in photoelectron angular distribution (CDAD) for ionization in molecules oriented in a single ‖JKJMJ> rotational eigenstate. These processes have been investigated also as two of the possible alternatives to photodissociation to determine orientational distribution function of rotationally state selected, oriented molecules. Expressions are derived which can be used to calculate ARPES and CDAD for such molecular species from ab initio methods or to analyze these experimentally observed spectra for extracting information about the degree of orientation of the molecular framework. These formulas are put in their simplest possible forms using the transformation properties of the molecular point group to their full advantage. The ionization amplitude is thus shown to decompose into a sum of transitions each involving the final state wave function belonging to an irreducible representation of the point group of the target molecule. It is found that, similar to the case of photodissociation, one can determine the rotational quantum number J purely from experimental photoionization data. Expressions developed herein are used to study ARPES and CDAD for ionization in a1 orbital of those rotationally state selected and oriented spherical top molecules which transform according to the Td point symmetry group. In this case, the detection-integrated cross section, singly differential in molecular orientation, is found to be independent of the photoionization dynamics and directly gives the molecular orientational function. The other ARPES and CDAD formulas are shown to depend upon the dynamics through the integrated partial cross section σ¯, the angularly asymmetry parameter β¯, the phase shift of the continuum waves representing the photoelectron, and the phase of the dipole transition amplitudes. The formulation presented in this paper sets a

  11. 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.

  12. 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.

  13. Fragment appearance energies in dissociative ionization of a sulfur hexafluoride molecule by electron impact

    NASA Astrophysics Data System (ADS)

    Demesh, Sh. Sh.; Zavilopulo, A. N.; Shpenik, O. B.; Remeta, E. Yu.

    2015-06-01

    Theoretical analysis of the fragment appearance energies corresponding to possible channels of formation of SF{/k +} fragments in dissociative ionization of the SF6 molecule by an electron impact is carried out. The total energies of neutral and ion molecular and atomic fragments are calculated using the theoretical methods of the GAMESS program complex. It is concluded that apart from dissociative ionization via autoionizing repulsive electronic states of the SF6 molecule, the excitation channels for SF{/k +} fragments and F2 molecules play a significant role, which leads to higher values of the observed fragment appearance energy as compared to theoretical values. The dependence of the energy corresponding to the formation of SF{/k +} c fragments on the number k of fluorine atoms is considered.

  14. 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.

  15. 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.

  16. The influence of a permanent dipole moment on the tunnelling ionization of a CO molecule

    NASA Astrophysics Data System (ADS)

    Kornev, Aleksei S.; Semiletov, Ivan M.; Zon, Boris A.

    2016-05-01

    We show that the linear Stark effect due to a molecule permanent dipole moment does not influence the rate of molecule ionization by laser radiation in the multiphoton limit. However, it may influence the ionization rate in the tunnelling limit. A CO molecule is considered as an example. Its valence orbitals have σ symmetry. In this case, the tunnel effect rate is maximal if the permanent dipole moment (the molecule axis) is oriented along the direction of the laser-wave electric field, and the role of the linear Stark effect is the most noticeable. This situation differs from that when the valence orbitals have π symmetry which we have considered previously (Kornev and Zon 2014 Laser Phys. 24 115302). In that case, the tunnel effect rate is maximal if the molecule axis is oriented perpendicularly to the electric field direction and the role of the linear Stark effect is less significant. We consider the tunnel effect in both dc and ac fields, accounting for perturbation of vibrational motion by an external field. We show that the influence of the permanent dipole moment does not vanish even after averaging the tunnelling rate over the molecule orientations.

  17. 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.

  18. 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.

  19. 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. PMID:11855960

  20. Imaging the electronic structure of valence orbitals in the XUV ionization of aligned molecules

    NASA Astrophysics Data System (ADS)

    Rouzée, Arnaud; Harvey, Alex G.; Kelkensberg, Freek; Brambila, Danilo; Kiu Siu, Wing; Gademann, Georg; Smirnova, Olga; Vrakking, Marc J. J.

    2014-06-01

    We present measurements of photoelectron angular distributions (PADs) for the ionization of aligned CO2 molecules by an extreme ultraviolet laser pulse (17-45 eV) that is produced via high-harmonic generation, and that is polarized perpendicularly to the alignment laser axis. Differential PADs are recorded by taking the difference between two measurements for aligned and anti-aligned molecules. The results are compared with ab initio multi-channel R-matrix calculations, which are extended to include the computation of PADs. The calculations agree very well with the experiment, and are resolved with respect to the internal state of the ion and the polarization of the ionizing laser field relative to the molecular frame. For a sufficiently high, but experimentally achievable degree of alignment, the nodal structure of the molecular orbital becomes visible in the PAD.

  1. 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.

  2. 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.

  3. 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.

  4. Alignment- and orientation-dependent strong-field ionization of molecules: Field-induced orbital distortion effects

    NASA Astrophysics Data System (ADS)

    Spiewanowski, Maciej Dominik; Madsen, Lars Bojer

    2015-05-01

    Strong-field ionization (SFI) is a starting point for many strong-field phenomena, e.g., high-order harmonic generation, as well as a source of fundamental information about the ionized target. Therefore, investigation of SFI of atoms and molecules has been the aim for research since the first strong laser pulses became available. We present a recently developed method, adiabatic strong-field approximation, to study ionization yields as a function of alignment angle for CO2, CO, and OCS molecules. We show that orbital distortion plays an important role in explaining the position and relative strength of maxima in the yields for both polar and nonpolar molecules, even for targets with low polarizabilities at low laser intensities. In particular, we report that for ionization of CO2 the maximum in ionization yield shifts towards the experimentally-measured maximum with respect to the strong-field approximation. For ionization of the CO molecule, not only does the theory predict the preferred direction of ionization correctly, but also the ratio between yields for the two molecular orientations where the electric field points either towards the C or towards the O end. Finally, we find that ionization of OCS is more probable for the laser pointing from the O end towards the S end. Work supported by the Natural Sciences and Engineering Research Council of Canada, the ERC-StG (Project No. 277767-TDMET), and the VKR center of excellence, QUS- COPE.

  5. Absolute effective cross sections of ionization of adenine and guanine molecules by electron impact

    NASA Astrophysics Data System (ADS)

    Shafranyosh, I. I.; Svida, Yu. Yu.; Sukhoviya, M. I.; Shafranyosh, M. I.; Minaev, B. F.; Baryshnikov, G. V.; Minaeva, V. A.

    2015-10-01

    Effective cross sections of the formation of positive ions of nitrous nucleic acids of adenine and guanine are determined by the crossed electron and molecular beam method in the energy interval from the threshold to 200 eV. It is found that the maximal value of the total cross section of adenine ionization is attained at an energy of 90 eV and is equal to (2.8 ± 0.6) × 10-15 cm2. The maximal value of the total cross section of guanine ionization is equal to (3.2 ± 0.7) × 10-15 cm2 and is observed at an energy of 88 eV. The energy ionization thresholds are determined, which amount to (8.8 ± 0.2) eV for adenine and to (8.3 ± 0.2) eV for guanine. The adenine and guanine mass spectra are measured. The absolute values of partial ionization cross sections of adenine and guanine molecules are determined.

  6. 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.

  7. Mass-Analyzed Threshold Ionization (MATI) Spectroscopy of Atoms and Molecules using VUV Synchrotron Radiation

    SciTech Connect

    Kostko, Oleg; Kim, Sang Kyu; Leone, Stephen R.; Ahmed, Musahid

    2009-01-28

    Mass-analyzed threshold ionization (MATI) spectroscopy using synchrotron radiation (Advanced Light Source, Lawrence Berkeley National Laboratory) has been performed for Ar, N2, O2, N2O, H2O, C2H2, and C6H6. MATI allows for a better determination of ionization energies compared to those derived from photoionization efficiency curves traditionally used in synchrotron photoionization mass spectrometry. The separation of the long-lived Rydberg state from the directly-formed prompt ion, essential for a meaningful MATI spectrum, has been accomplished by employing an arrangement of ion optics coupled to unique electric-field pulsing schemes. For Ar, a number of resolved bands below the ionization energy are observed, and these are ascribed to high-n,l Rydberg states prepared in the MATI scheme. The first vibrational stateresolved MATI spectra of N2 and O2 are reported and spectral characteristics are discussed in comparison with previously-reported threshold photoelectron spectroscopic studies. While MATI performed with synchrotron radiation is intrinsically less sensitive compared to laser based sources, this work demonstrates that MATI spectroscopy performed with widely tunable VUV radiation is a complementary technique for studying the ionization spectroscopy of polyatomic molecules.

  8. Accurate Ionization Potentials and Electron Affinities of Acceptor Molecules IV: Electron-Propagator Methods.

    PubMed

    Dolgounitcheva, O; Díaz-Tinoco, Manuel; Zakrzewski, V G; Richard, Ryan M; Marom, Noa; Sherrill, C David; Ortiz, J V

    2016-02-01

    Comparison of ab initio electron-propagator predictions of vertical ionization potentials and electron affinities of organic, acceptor molecules with benchmark calculations based on the basis set-extrapolated, coupled cluster single, double, and perturbative triple substitution method has enabled identification of self-energy approximations with mean, unsigned errors between 0.1 and 0.2 eV. Among the self-energy approximations that neglect off-diagonal elements in the canonical, Hartree-Fock orbital basis, the P3 method for electron affinities, and the P3+ method for ionization potentials provide the best combination of accuracy and computational efficiency. For approximations that consider the full self-energy matrix, the NR2 methods offer the best performance. The P3+ and NR2 methods successfully identify the correct symmetry label of the lowest cationic state in two cases, naphthalenedione and benzoquinone, where some other methods fail. PMID:26730459

  9. 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.

  10. Vascular activation of adhesion molecule mRNA and cell surface expression by ionizing radiation.

    PubMed

    Heckmann, M; Douwes, K; Peter, R; Degitz, K

    1998-01-10

    During cutaneous inflammatory reactions the recruitment of circulating leukocytes into the tissue critically depends on the regulated expression of endothelial cell adhesion molecules (CAMs). Various proinflammatory stimuli upregulate endothelial CAMs, including cytokines and UV irradiation. We have investigated the effects of ionizing radiation (IR) on endothelial CAM expression. Organ cultures of normal human skin as well as cultured human dermal microvascular endothelial cells (HDMEC) were exposed to IR. Expression of three major endothelial CAMs was studied in skin organ cultures by immunohistochemistry and in cell culture by Northern blot analysis and flow cytometry. In skin organ cultures vascular immunoreactivity for ICAM-1, E-selectin, and VCAM-1 was strongly induced 24 h after exposure to 5 or 10 Gy of IR, while immunoreactivity for CD31/PECAM-1, a constitutively expressed endothelial cell adhesion molecule, remained unchanged. In cultured HDMEC IR upregulated ICAM-1, VCAM-1, and E-selectin mRNAs and cell surface expression in a time- and dose-dependent fashion. Cellular morphology and viability remained unaltered by IR up to 24 h postirradiation. This study characterizes microvascular activation of adhesion molecule expression in response to ionizing radiation in a clinically relevant IR dose range. The findings also underscore the ability of endothelial cells to integrate environmental electromagnetic stimuli. PMID:9457067

  11. 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.

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

    NASA Astrophysics Data System (ADS)

    Gazibegović-Busuladžić, A.; Hasović, E.; Busuladžić, M.; Milošević, D. B.; Kelkensberg, F.; Siu, W. K.; Vrakking, M. J. J.; Lépine, F.; Sansone, G.; Nisoli, M.; Znakovskaya, I.; Kling, M. F.

    2011-10-01

    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 N2 and O2 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.

  13. Role of Coulomb repulsion in correlated-electron emission from a doubly excited state in nonsequential double ionization of molecules

    NASA Astrophysics Data System (ADS)

    Huang, Cheng; Guo, Wenliang; Zhou, Yueming; Wu, Zhengmao

    2016-01-01

    With the classical ensemble model, we investigate nonsequential double ionization of aligned molecules by few-cycle laser pulses at low intensity, where the two electrons finally are ionized through a transition doubly excited state induced by recollision. The correlated electron momentum distribution of parallel molecules exhibits the line-shaped structure parallel to the diagonal. Our analysis indicates that besides the ionization time difference of two electrons from the doubly excited state, the final-state e-e Coulomb repulsion plays a vital role in the formation of the line-shaped structural momentum distribution. For perpendicular molecules, due to the prominent near half-cycle ionization time difference between the two electrons from the doubly excited state, the momentum distribution shows clear anticorrelation behavior.

  14. 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.

  15. 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. PMID:26349643

  16. Ion/molecule reaction and ion evaporation in atmospheric pressure spray ionization

    NASA Astrophysics Data System (ADS)

    Hirabayashi, Atsumu; Takada, Yasuaki; Kambara, Hideki; Umemura, Yuta; Ohta, Hitoshi; Ito, Haruhiko; Kuchitsu, Kozo

    1992-12-01

    The positive ions produced in atmospheric pressure spray ionization of ammonia, alanine and sucrose in aqueous solution were detected with a double-focusing mass spectrometer. The relative intensities of the quasi-molecular ions of ammonia, NH+4 (H2O)n (n = 0-3), were found to be proportional to the concentration of the ammonia solution and to increase with increasing distance d between the nozzle tip and the sample aperture of the mass spectrometer; this observation shows that the ammonia molecule is produced by the spray and is protonated at atmospheric pressure by a proton transfer reaction with the hydronium ion and its hydrated clusters. The observed dependences of the relative intensities of the protonated alanine molecules from alanine solution and the cationized sucrose molecules from sucrose solution on d show that some part of these quasi-molecular ions are also produced by the ion/molecule reaction in the gas phase. However, their dependences on the concentration, which are steeper than that in the ammonia case, indicate that a significant proportion of these ions are produced by ion evaporation from a droplet or liquid.

  17. 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.

  18. Ionization and Desorption of Molecule Ice Stimulated by X-Rays in Circumstellar Envelopes

    NASA Astrophysics Data System (ADS)

    Mendoza, E. F.; Almeida, G.; Wolff, W.; Andrade, D. P. P.; Rocco, M. L. M.; Boechat-Roberty, H. M.

    2012-12-01

    The HCN and C2H2 molecules present in protoplanetary disks can form the Nitrogen-containing cyclic organic molecules (N-heterocycles) that play important roles in terrestrial biology, for example as the nucleobases in genetic material. In this work the ionization, dissociation and desorption processes of pyrimidine ice, a nucleotide precursor molecule, were experimentally studied applying the time-of-flight mass spectrometry technique, in order to evaluate their destruction pathways in protoplanetary disks. These processes were stimulated by soft X-rays from 397 to 430 eV delivered by synchrotron light source. The photodesorption ion yield (ion photon-1) of several ions such as HCN+, C4H2+, HC3NH+, and C3H3N+ among other ionic fragments were determined. Considering that TW Hydrae has an integrated X-ray luminosity (LX) from 0.2 to 2 keV of ˜ 1 × 1030 erg s-1, the ion flux (ion cm-2 s-1) desorbed from the grain surface and the ion production rate (ion cm-3 s-1) were determined as a function of the distance from the central star. The results show that ionic species are formed from ice due to photons interaction, highlighting the role of the ice chemistry in the molecular enrichment in protoplanetary disks.

  19. 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.

  20. 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.

  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. PMID:24050350

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

    NASA Astrophysics Data System (ADS)

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

    2013-09-01

    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.

  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. 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.

  5. Spectrophotometric pKa determination of ionizable pharmaceuticals: Resolution of molecules with weak pH-dependent spectral shift.

    PubMed

    Dohoda, Deren; Tsinman, Konstantin; Tsinman, Oksana; Wang, Haotian; Tam, Kin Y

    2015-10-10

    The extent of ionization of a drug molecule at different pH values can be characterized by its pKa (acid dissociation constants). It is an important parameter in pharmaceutical development to rationalize the physiochemical and biopharmaceutical properties of the drug molecule. UV titration for pKa determination is one of the popular methods. The success of this method requires the molecule exhibiting strong pH-dependent spectral shift related to the ionization process. Depending on the proximity between the ionizable group and the chromophore, the spectral shift may not be strong enough to warrant a successful determination. In a previous study, it has been reported that a distance of three σ bonds between the chromophore and the ionizable group was the limit for a precise pKa determination. In this work, a UV titration method for pKa determination, with a particular emphasis on molecules with weak pH-dependent spectral shift is investigated. It has been shown that the pKa values determined from this study are in good agreement with those determined using potentiometric method and literature data (R(2)=0.998). Our methodology revealed that successful pKa determination is feasible even with a separation distance of five σ bonds between the chromophore and the ionizable group. PMID:26026267

  6. 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.

  7. 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

  8. 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.

  9. 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

  10. 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

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

    DOE PAGESBeta

    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.

  12. 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.

  13. 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.

  14. 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.

  15. 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

    NASA Astrophysics Data System (ADS)

    Busuladžić, M.; Gazibegović-Busuladžić, A.; Milošević, D. B.

    2009-07-01

    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 O2 molecule (characterized by πg symmetry) the maximum yield is observed for some value of the ellipticity ɛ different from zero. On the other hand, in the same circumstances, the N2 molecule (σg) behaves as an atom, i.e., the yield is maximum for ɛ=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.

  16. 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.

  17. 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.

  18. Ion-molecule reactions of oxygenated chemical ionization reagents with vincamine.

    PubMed

    Bauerle, G F; Hall, B J; Tran, N V; Brodbelt, J S

    1996-03-01

    The ion-molecule reactions of ions from acetone, dimethyl ether, 2-methoxyethanol, and vinyl methyl ether with vincamine were investigated. Reactions with dimethyl ether result in [M+13](+) and [M+45](+) products, reactions with 2-methoxyethanol produce [M+13](+) and [M+89](+) ions, and reactions with acetone or vinyl methyl ether ions generate predominantly [M+43](+) ions. Collision-activated dissociation and deuterium labeling experiments allowed speculation about the product structures and mechanisms of dissociation. The methylene substitution process was shown to occur at the hydroxyl oxygen and the phenyl ring of vincamine for dimethyl ether reactions, but the methylene substitution process was not favored at the hydroxyl oxygen for the 2-methoxyethanol reactions, instead favored at the 12 phenyl position. The reaction site is likely different for the 2-methoxyethanol ion due to its capability for secondary hydrogen-bonding interactions. For the [M+45](+) and [M+89](+) ions, evidence suggests that charge-remote fragmentation processes occur from these products. In general, the use of dimethyl ether ions or 2-methoxyethanol ions for ionmolecule reactions prove highly diagnostic for the characterization of vincamine; both molecular weight and structural information are obtained. Limits of detection for vincamine with dimethyl ether chemical ionization via this technique on a benchtop ion trap gas chromatography-tandem mass spectrometer are in the upper parts per trillion range. PMID:24203296

  19. Metal-assisted polyatomic SIMS and laser desorption/ionization for enhanced small molecule imaging of bacterial biofilms.

    PubMed

    Dunham, Sage J B; Comi, Troy J; Ko, Kyungwon; Li, Bin; Baig, Nameera F; Morales-Soto, Nydia; Shrout, Joshua D; Bohn, Paul W; Sweedler, Jonathan V

    2016-06-01

    Mass spectrometry imaging (MSI) has become an important analytical tool for many sectors of science and medicine. As the application of MSI expands into new areas of inquiry, existing methodologies must be adapted and improved to meet emerging challenges. Particularly salient is the need for small molecule imaging methods that are compatible with complex multicomponent systems, a challenge that is amplified by the effects of analyte migration and matrix interference. With a focus on microbial biofilms from the opportunistic pathogen Pseudomonas aeruginosa, the relative advantages of two established microprobe-based MSI techniques-polyatomic secondary ion mass spectrometry (SIMS) and laser desorption/ionization-are compared, with emphasis on exploring the effect of surface metallization on small molecule imaging. A combination of qualitative image comparison and multivariate statistical analysis demonstrates that sputtering microbial biofilms with a 2.5 nm layer of gold selectively enhances C60-SIMS ionization for several molecular classes including rhamnolipids and 2-alkyl-quinolones. Metallization also leads to the reduction of in-source fragmentation and subsequent ionization of media-specific background polymers, which improves spectral purity and image quality. These findings show that the influence of metallization upon ionization is strongly dependent on both the surface architecture and the analyte class, and further demonstrate that metal-assisted C60-SIMS is a viable method for small molecule imaging of intact molecular ions in complex biological systems. PMID:26945568

  20. 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.

  1. 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.

  2. 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.

  3. 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.

  4. 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

  5. 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

  6. 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.

  7. 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.

  8. 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.

  9. Spectral Evidence for Ionization in Air-Filled Glow Discharge Tubes: Application to Sprites

    NASA Astrophysics Data System (ADS)

    Armstrong, R. A.; Williams, E. R.; Golka, R. K.; Williams, D. R.

    2001-12-01

    The question of ionization in sprites and the evidence for VLF backscatter from sprites has motivated a quantitative spectral analysis of the various (classical) regions of the glow discharge tube under DC excitation and at air densities appropriate for sprites in the mesosphere. A PR-650 colorimeter (Photo Research, Inc.) has enabled calibrated irradiance measurements for localized zones along the axis of the discharge tube--in the dominantly blue negative glow, in the Faraday dark space and in the red/pink positive column. Consistent with historical nomenclature, nitrogen first and second positive emission is dominant in the positive column (associated with neutral N2), and nitrogen first negative emission, with a prominent peak at 4278 A, is dominant in the blue negative glow (associated with ionized N2+). Whereas nitrogen first and second positive emission are also detected in the negative glow, no spectral evidence for ionization (no 4279, no 3914, no Meinel) is found in the red/pink positive column. This negative result is attributed not to an absence of ionization in the positive column, but rather to a sparse population of N2+ relative to neutral nitrogen in this region, and to the prominent emission in the blue part of the spectrum due to nitrogen second positive. A similar interpretation may be appropriate for the time-integrated spectra from the red body of sprites, also lacking direct evidence for ionization.

  10. 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.

  11. 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.

  12. 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.

  13. 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.

  14. 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.

  15. Detection of Ultracold Ground-State Molecules by One- and Two-Color Resonance-Enhanced Two-Photon Ionization

    NASA Astrophysics Data System (ADS)

    Li, Zhonghao; Ji, Zhonghua; Zhang, Xiang; Yuan, Jinpeng; Zhao, Yanting; Xiao, Liantuan; Jia, Suotang

    2016-08-01

    One- and two-color resonance-enhanced two-photon ionization (RETPI) is used to detect ultracold ground-state RbCs molecules which are formed via short-range photoassociation from laser-cooled atoms. The transition from the X1Σ+(v = 0) state to the 21Π(v = 10) state of ultracold RbCs molecules shows the consistence of one- and two-color RETPI. A multi-photon photoionization rate model is introduced to interpret the dependence of molecular ion intensity on photoionized laser energy, and can be used to verify the photoionization scheme. This photoionization rate model can be expanded to multi-color photoionization for all kinds of atoms and molecules, which is a powerful method of determining the photoionization scheme.

  16. 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)

  17. 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.

  18. Surface ionization of terpene hydrocarbons

    SciTech Connect

    Zandberg, E.Y.; Nezdyurov, A.L.; Paleev, V.I.; Ponomarev, D.A.

    1986-09-01

    By means of a surface ionization indicator for traces of materials in the atmosphere it has been established that many natural materials containing terpenes and their derivatives are ionized on the surface of heated molybdenum oxide at atmospheric air pressure. A mass-spectrometer method has been used to explain the mechanism of ionization of individual terpene hydrocarbons and to establish its principles. The ionization of ..cap alpha..-pinene, alloocimene, camphene, and also adamantane on oxidized tungsten under vacuum conditions has been investigated. The ..cap alpha..-pinene and alloocimene are ionized by surface ionization but camphene and adamantane are not ionized under vacuum conditions. The surface ionization mass spectra of ..cap alpha..-pinene and alloocimene are of low line brightness in comparison with electron ionization mass spectra and differ between themselves. The temperature relations for currents of the same compositions of ions during ionization of ..cap alpha..-pinene and alloocimene are also different, which leads to the possibility of surface ionization analysis of mixtures of terpenes being ionized. The ionization coefficients of alloocimene and ..cap alpha..-pinene on oxidized tungsten under temperatures optimum for ionization and the ionization potentials of alloocimene molecules and of radicals (M-H) of both compounds have been evaluated.

  19. 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.

  20. 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.

  1. 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

  2. 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.

  3. 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

  4. 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…

  5. 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.

  6. 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.

  7. 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.

  8. Gold nanoparticles assisted laser desorption/ionization mass spectrometry and applications: from simple molecules to intact cells.

    PubMed

    Abdelhamid, Hani Nasser; Wu, Hui-Fen

    2016-07-01

    Gold nanoparticles (AuNPs) assisted laser desorption/ionization mass spectrometry (GALDI-MS) provided new horizons and offered many functions for various applications. This review summarized AuNPs applications for analytical, biotechnology and proteomics. AuNPs efficiently absorbed the laser radiation and transferred the energy to the analyte for the desorption/ionization process. The unique features of AuNPs such as large surface area and high absorption coefficient lead not only to high resolution, low interference and low limit of detection, but also offered selective detection for certain species. AuNPs provided an excellent surface for the analysis of several species such as small molecules, biomarkers, proteins and cells (pathogenic bacteria or cancer cells). AuNPs played many roles such as surface for LDI-MS, probe and stationary phase for separation or preconcentration. AuNPs modified various surface chemistry was applied for a wide range of different wavelength. AuNPs severed as a source of Au(+) ions that were suitable for analyte cationisation. Characterization of Au nanoclusters (AuNCs) by mass spectrometry, pros and cons were also highlighted. Graphical Abstract Schematic representation of the analysis by Gold Nanoparticles Assisted Laser Desorption/Ionization Mass Spectrometry (GALDI-MS). PMID:26973236

  9. 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.

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

    PubMed

    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 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 CH(x)(HR), x = 1-3, and H2(HR) were also observed. The production of HR fragments is attributed to dissociation of CH4(+) and CH4(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. PMID:26395703

  11. Isomer and Fluorination Effects among Fluorine Substituted Hydrocarbon C3/C4 Molecules in Electron Impact Ionization

    NASA Astrophysics Data System (ADS)

    Patel, U. R.; Joshipura, K. N.

    2015-05-01

    Electron collision processes are very important in both man-made and natural plasmas, for determining the energy balances and transport properties of electrons. Electron -molecule scattering leading to ionization represents one of the most fundamental processes in collision physics. In the gas phase, the total efficiency of the process is described by the absolute total electron impact ionization cross section. Carbon based materials are some of the widely used materials for a divertor plate and magnetically confined fusion devices. In the ``ITER,'' it is very important for steady state operation to have an estimate of the lifetime of carbon plasma facing components. Apart from fusion plasma relevance, the present theoretical study is very important in modeling and controlling other electron assisted processes in many areas. Hydrocarbons play an important role for plasma diagnostics as impurities in the Tokamak fusion divertor, as seed gases for the production of radicals and ions in low temperature plasma processing. Fluorine substituted hydrocarbons (perfluorocarbons) are important as reactants in plasma assisted fabrication processes. In the present work, we have calculated total ionization cross sections Qion for C3/C4 Hydrocarbon isomers by electron impact, and comparisons are made mutually to observe isomer effect. Comparisons are also made by substituting H atom by F atom and revealing fluorination effect. The present calculations are quite significant owing to the lack of experimental data, with just an isolated previous theoretical work in some cases.

  12. 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.

  13. Theory of coherent polarization anisotropy in time-resolved two-photon ionization of isolated molecules. Effects of Coriolis couplings

    NASA Astrophysics Data System (ADS)

    Sato, S.; Nomura, Y.; Fujimura, Y.

    1987-09-01

    Effects of vibration-rotation (Coriolis) couplings on the coherent polarization anisotropy are theoretically studied in a time-resolved two-photon ionization of a symmetric top molecule. This polarization anisotropy originates from a coherent excitation of the resonant rovibronic molecular eigenstates (rovibronic coherence) whose zeroth order states are mixed through the Coriolis coupling. Expressions for the time-dependent degree of polarization after the coherent excitation of the rovibronic states produced by the Coriolis coupling are derived as a function of the delay time in the pump-probe two-photon ionization. Model calculations of the time-dependent degree of polarization as well as the probabilities of the two-photon ionization are performed to demonstrate the Coriolis coupling effects in the low excess energy regions of the resonant intermediate state. It is shown that oscillatory behaviors in the time-dependent degree of polarization should be observed as a result of the creation of the rovibronic coherence. It is demonstrated that oscillations of the degree of polarization involve both contribution of the purely rotational J-coherence and that of the rovibronic coherence in the resonant manifold when the rotational branches are coherently excited and the characteristic rotation-vibration interaction energy is larger than a typical free rotational energy under jet-cooled condition.

  14. 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.

  15. 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

  16. (e,2e) ionization of helium and the hydrogen molecule: signature of two-centre interference effects

    NASA Astrophysics Data System (ADS)

    Staicu Casagrande, E. M.; Naja, A.; Mezdari, F.; Lahmam-Bennani, A.; Bolognesi, P.; Joulakian, B.; Chuluunbaatar, O.; Al-Hagan, O.; Madison, D. H.; Fursa, D. V.; Bray, I.

    2008-01-01

    Relative (e,2e) triply differential cross sections (TDCS) are measured for the ionization of the helium atom and the hydrogen molecule in coplanar asymmetric geometry at a scattered electron energy of 500 eV and ejected electron energies of 205, 74 and 37 eV. The He experimental results are found to be in very good agreement with convergent close-coupling calculations (CCC). The H2 experimental results are compared with two state-of-the-art available theoretical models for treating differential electron impact ionization of molecules. Both models yield an overall good agreement with experiments, except for some intensity deviations in the recoil region. Similar (e,2e) works were recently published on H2 with contrasted conclusions to the hypothesis that the two H nuclei could give rise to an interference pattern in the TDCS structure. Murray (2005 J. Phys. B: At. Mol. Opt. Phys. 38 1999) found no evidence for such an effect, whereas Milne-Brownlie et al (2006 Phys. Rev. Lett. 96 233201) reported its indirect observation. In this work, based on a direct comparison between experimental results for He and H2, we observe an oscillatory pattern due to these interference effects, and for the first time the destructive or constructive character of the interference is observed, depending on the de Broglie wavelength of the ejected electron wave. The experimental finding is in good agreement with the theoretical prediction by Stia et al (2003 J. Phys. B: At. Mol. Opt. Phys. 36 L257).

  17. Phloroglucinol protects small intestines of mice from ionizing radiation by regulating apoptosis-related molecules: a comparative immunohistochemical study.

    PubMed

    Ha, Danbee; Bing, So Jin; Cho, Jinhee; Ahn, Ginnae; Kim, Dae Seung; Al-Amin, Mohammad; Park, Suk Jae; Jee, Youngheun

    2013-01-01

    Phloroglucinol (PG) is a phenolic compound isolated from Ecklonia cava, a brown algae abundant on Jeju island, Korea. Previous reports have suggested that PG exerts antioxidative and cytoprotective effects against oxidative stress. In this study, we confirmed that PG protected against small intestinal damage caused by ionizing radiation, and we investigated its protective mechanism in detail. Regeneration of intestinal crypts in the PG-treated irradiated group was significantly promoted compared with that in irradiated controls. The expression level of proapoptotic molecules such as p53, Bax, and Bak in the small intestine was downregulated and that of antiapoptotic molecules such as Bcl-2 and Bcl-X(S/L) was augmented in the PG-treated group. On histological observation of the small intestine, PG inhibited the immunoreactivity of p53, Bax, and Bak and increased that of Bcl-2 and Bcl-X(S/L). These results demonstrate the protective mechanisms of PG in mice against intestinal damage from ionizing radiation, providing the benefit of raising the apoptosis threshold of jejunal crypt cells. PMID:23117934

  18. A new approach to the determination of air kerma using primary-standard cavity ionization chambers

    NASA Astrophysics Data System (ADS)

    Burns, D. T.

    2006-02-01

    A consistent formalism is presented using Monte Carlo calculations to determine the reference air kerma from the measured energy deposition in a primary-standard cavity ionization chamber. A global approach avoiding the use of cavity ionization theory is discussed and its limitations shown in relation to the use of the recommended value for W. The role of charged-particle equilibrium is outlined and the consequent requirements placed on the calculations are detailed. Values for correction factors are presented for the BIPM air-kerma standard for 60Co, making use of the Monte Carlo code PENELOPE, a detailed geometrical model of the BIPM 60Co source and event-by-event electron transport. While the wall correction factor kwall = 1.0012(2) is somewhat lower than the existing value, the axial non-uniformity correction kan = 1.0027(3) is significantly higher. The use of a point source in the evaluation of kan is discussed. A comparison is made of the calculated dose ratio with the Bragg-Gray and Spencer-Attix stopping-power ratios, the results indicating a preference for the Bragg-Gray approach in this particular case. A change to the recommended value for W of up to 2 parts in 103 is discussed. The uncertainties arising from the geometrical models, the use of phase-space files, the radiation transport algorithms and the underlying radiation interaction coefficients are estimated.

  19. Large-angle ionization chambers for brachytherapy air-kerma-strength measurements

    NASA Astrophysics Data System (ADS)

    Culberson, Wesley S.

    There has been a significant increase in the use of low-energy photon-emitting radionuclides in the past decade to treat cancer with a special form of radiation therapy called brachytherapy. For treating prostate cancer, brachytherapy sources are approximately the size of a grain of rice and are normally radioactive 125I or 103Pd sources encapsulated in titanium or plastic. Although these sources have proven effective in the treatment of cancer, the clinical dosimetry is difficult due to the unique varieties available and their typically. A large-angle free-air chamber at the National Institute of Standards and Technology (NIST) called the Wide-Angle Free-Air Chamber (WAFAC) is the current standard for measuring the strength of low-energy photon-emitting radionuclides for brachytherapy. This chamber has served the clinical medical physics community well and is a significant improvement over previous standards. However, it has some shortcomings. This thesis describes the development of a new large-angle ionization chamber at the University of Wisconsin called the Variable-Aperture Free-Air Chamber (VAFAC) to measure brachytherapy sources with extended capabilities. This chamber is constructed to explore characteristics in the calibration of brachytherapy seeds by quantifying potential variations caused by anisotropy and the change in response with integration angle. In addition, the characterization of yet another large-angle free-air chamber called the Grossvolumen Extrapolationskammer (GROVEX) in the German national standards institute Physikalisch-Technische Bundesanstalt (PTB) is also presented. The objective of this thesis is to present improved measurement techniques with free-air ionization chambers that will improve the accuracy of the dose delivered to patients. First, it will be shown that the UW VAFAC is capable of measuring conventional 125I or 103Pd seeds as well as longer sources, coiled sources, and miniature x-ray tubes. Additionally, the VAFAC

  20. Ionizing radiation mediates expression of cell adhesion molecules in distinct histological patterns within the lung.

    PubMed

    Hallahan, D E; Virudachalam, S

    1997-06-01

    Inflammatory cell infiltration of the lung is a predominant histopathological change that occurs during radiation pneumonitis. Emigration of inflammatory cells from the circulation requires the interaction between cell adhesion molecules on the vascular endothelium and molecules on the surface of leukocytes. We studied the immunohistochemical pattern of expression of cell adhesion molecules in lungs from mice treated with thoracic irradiation. After X-irradiation, the endothelial leukocyte adhesion molecule 1 (ELAM-1; E-selectin) was primarily expressed in the pulmonary endothelium of larger vessels and minimally in the microvascular endothelium. Conversely, the intercellular adhesion molecule 1 (ICAM-1; CD54) was expressed in the pulmonary capillary endothelium and minimally in the endothelium of larger vessels. Radiation-mediated E-selectin expression was first observed at 6 h, whereas ICAM-1 expression initially increased at 24 h after irradiation. ICAM-1 and E-selectin expression persisted for several days. P-selectin is constitutively expressed in Weibel-Palade bodies in the endothelium, which moved to the vascular lumen within 30 min after irradiation. P-selectin was not detected in the pulmonary endothelium at 6 h after irradiation. The radiation dose required for increased cell adhesion molecule expression within the pulmonary vascular endothelium was 2 Gy, and expression increased in a dose-dependent manner. These data demonstrate that ICAM-1 and E-selectin expression is increased in the pulmonary endothelium following thoracic irradiation. The pattern of expression of E-selectin, P-selectin, and ICAM-1 is distinct from one another. PMID:9187101

  1. 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

  2. Spatially resolved analysis of small molecules by matrix-assisted laser desorption/ionization mass spectrometric imaging (MALDI-MSI).

    PubMed

    Peukert, Manuela; Matros, Andrea; Lattanzio, Giuseppe; Kaspar, Stephanie; Abadía, Javier; Mock, Hans-Peter

    2012-02-01

    • Matrix-assisted laser desorption/ionization mass spectrometric imaging (MALDI-MSI) of tissues provides the means to analyse the spatial distributions of small molecules and proteins within tissues. This imaging technique is commonplace in medicinal and pharmaceutical research, but its application in plant science is very recent. Broader introduction requires specific adaptations for plant tissues. Sample preparation is of paramount importance in order to obtain high-quality spectra providing sufficient spatial resolution for compounds. Optimization is required for sectioning, choice of matrix and means of matrix deposition. • Here, we present our current protocols for the detection of small molecules in cryodissected immature barley (Hordeum vulgare) grains and tobacco (Nicotiana tabacum) roots. • Examples of MALDI-MSI measurements are provided, and the level of reproducibility across biological replicates is addressed. Furthermore, our approaches for the validation of distribution patterns and for the identification of molecules are described. • Finally, we discuss how MALDI-MSI can contribute to applied plant research. PMID:22126099

  3. 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

  4. 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

  5. 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

  6. 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.

  7. Experimental and Theoretical Fully differential cross sections for electron impact ionization of phenol molecules

    NASA Astrophysics Data System (ADS)

    Ali, Esam; Jones, D.; Silva, G.; Chiari, L.; Neves, R.; Lopes, M.; Brunger, M.; Ning, C.; Madison, D.

    2014-10-01

    Experimental and theoretical Fully Differential Cross Sections (FDCS) are presented for 250 eV electron impact ionization of the highest and next highest occupied molecular orbitals (HOMO and NHOMO). Theoretical results are compared with experiment for in plane scattering with projectile scattering angles of 5°, 10°, and 15°. Different theoretical models are examined - the molecular 3 body distorted wave (M3DW), and the distorted wave Born approximation (DWBA), with the effects of the post collision interaction (PCI) treated either exactly or with the Ward-Macek approximations. These approximations show good agreement with experimental data for binary peaks. However, for the recoil peak region, experiment finds a noticeable peak while theory predicts no peak. No recoil peak suggests no (or very weak) nuclear scattering, so we have investigated the importance of nuclear scattering by moving the nuclei closer to the center of mass. Work supported by NSF and the XSEDE.

  8. Single ionization of hydrogen molecules by fast protons as a function of the molecular alignment

    SciTech Connect

    Johnson, Nora G.; Mello, R. N.; Lundy, Michael E.; Kapplinger, J.; Wells, E.; Parke, Eli; Carnes, K. D.; Ben-Itzhak, I.

    2005-11-15

    Relative cross sections for the 4 MeV H{sup +}+D{sub 2} ({sup 1}{sigma}{sub g}{sup +}){yields}H{sup +}+D{sub 2}{sup +}(1s{sigma})+e{sup -} ionization process were measured as a function of the molecular alignment during the interaction. The angle between the molecular axis and the projectile was obtained by using a momentum imagining technique and isolating the events in which the D{sub 2}{sup +}(1s{sigma}) ions are excited to the vibrational continuum and subsequently dissociate. While anisotropic cross sections have been observed in the past for a number of collision processes involving both target electrons, the one electron process investigated here is isotropic within our experimental uncertainties.

  9. 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

  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. Measurement of the First Townsend's Ionization Coefficients in Helium, Air, and Nitrogen at Atmospheric Pressure

    NASA Astrophysics Data System (ADS)

    Ran, Junxia; Luo, Haiyun; Yue, Yang; Wang, Xinxin

    2014-07-01

    In the past the first Townsend’s ionization coefficient α could only be measured with Townsend discharge in gases at low pressure. After realizing Townsend discharge in some gases at atmospheric pressure by using dielectric barrier electrodes, we had developed a new method for measuring α coefficient at atmospheric pressure, a new optical method based on the discharge images taken with ICCD camera. With this newly developed method α coefficient in helium, nitrogen and air at atmospheric pressure were measured. The results were found to be in good agreement with the data obtained at lower pressure but same reduced field E/p by other groups. It seems that the value of α coefficient is sensitive to the purity of the working gas.

  12. Accurate Ionization Potentials and Electron Affinities of Acceptor Molecules II: Non-Empirically Tuned Long-Range Corrected Hybrid Functionals.

    PubMed

    Gallandi, Lukas; Marom, Noa; Rinke, Patrick; Körzdörfer, Thomas

    2016-02-01

    The performance of non-empirically tuned long-range corrected hybrid functionals for the prediction of vertical ionization potentials (IPs) and electron affinities (EAs) is assessed for a set of 24 organic acceptor molecules. Basis set-extrapolated coupled cluster singles, doubles, and perturbative triples [CCSD(T)] calculations serve as a reference for this study. Compared to standard exchange-correlation functionals, tuned long-range corrected hybrid functionals produce highly reliable results for vertical IPs and EAs, yielding mean absolute errors on par with computationally more demanding GW calculations. In particular, it is demonstrated that long-range corrected hybrid functionals serve as ideal starting points for non-self-consistent GW calculations. PMID:26731340

  13. 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.

  14. 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.

  15. Excitation two-center interference and the orbital geometry in laser-induced nonsequential double ionization of diatomic molecules

    SciTech Connect

    Shaaran, T.; Augstein, B. B.; Figueira de Morisson Faria, C.

    2011-07-15

    We address the influence of the molecular orbital geometry and of the molecular alignment with respect to the laser-field polarization on laser-induced nonsequential double ionization of diatomic molecules for different molecular species, namely N{sub 2} and Li{sub 2}. We focus on the recollision excitation with subsequent tunneling ionization (RESI) mechanism, in which the first electron, upon return, promotes the second electron to an excited state, from where it subsequently tunnels. We assume that both electrons are initially in the highest occupied molecular orbital (HOMO) and that the second electron is excited to the lowest unoccupied molecular orbital (LUMO). We show that the electron-momentum distributions exhibit interference maxima and minima due to the electron emission at spatially separated centers. We provide generalized analytical expressions for such maxima or minima, which take into account s-p mixing and the orbital geometry. The patterns caused by the two-center interference are sharpest for vanishing alignment angle and get washed out as this parameter increases. Apart from that, there exist features due to the geometry of the LUMO, which may be observed for a wide range of alignment angles. Such features manifest themselves as the suppression of probability density in specific momentum regions due to the shape of the LUMO wave function, or as an overall decrease in the RESI yield due to the presence of nodal planes.

  16. Reliable Formation of Single Molecule Junctions with Air-Stable Diphenylphosphine Linkers

    SciTech Connect

    Parameswaran, R.; Hybertsen, M.; Widawsky, J.R.; Vázquez H.; Park, Y.S.; Boardman, B.M.; Nuckolls, C.; Steigerwald, M.L.; Venkataraman, L.

    2010-07-15

    We measure the conductance of single Au-molecule-Au junctions with a series of air-stable diphenylphosphine-terminated molecules using the scanning tunneling microscope-based break junction technique. Thousands of conductance versus displacement traces collected for each molecule are used to statistically analyze junction conductance and evolution upon elongation. Measured conductances for a series of alkane-based molecules exhibit an exponential decrease with increasing length, as expected for saturated molecules, with a tunneling decay constant of 0.98 {+-} 0.04. Measurements of junction elongation indicate strong metal-molecule binding, with a length that increases with the number of methylene groups in the backbone. Measured conductance histograms for four molecules with short, unsaturated backbones (e.g., benzene) are much broader with less well-defined peaks. These measurements are supported by density function theory calculations. The phosphine binds selectively to under-coordinated gold atoms through a donor-acceptor bond with a binding energy of about 1 eV. The calculated tunnel coupling correlates very well with experiment.

  17. 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

  18. 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

  19. Experimental and Theoretical Fully differential cross sections for electron impact ionization of furfuryl molecules

    NASA Astrophysics Data System (ADS)

    Ali, Esam; Jones, Darryl; Nixon, Kate; Ning, Chuangang; Brunger, Michael; Murray, Andrew; Madison, Don

    2015-09-01

    Experimental and theoretical Fully Differential Cross Sections (FDCS) are presented for 250 eV electron impact ionization of the highest and next highest occupied molecular orbitals (HOMO and NHOMO). Theoretical results are compared with experiment for in plane scattering with projectile scattering angles of 5°, 10°, and 15°. Different theoretical models are examined - the molecular 3 body distorted wave (M3DW), and the distorted wave Born approximation (DWBA), with the effects of the post collision interaction (PCI) treated either exactly or with the Ward-Macek approximations. These approximations show good agreement with experimental data for binary peaks. However, for the recoil peak region, experiment finds a noticeable peak while theory predicts no peak. No recoil peak suggests no (or very weak) nuclear scattering, so we have investigated the importance of nuclear scattering by moving the nuclei closer to the center of mass. This work is supported by the US National Science Foundation under Grant No. PHY-1068237 and XSEDE resources provided by the Texas Advanced Computing Center (Grant No. TG-MCA07S029).

  20. Accurate Ionization Potentials and Electron Affinities of Acceptor Molecules III: A Benchmark of GW Methods.

    PubMed

    Knight, Joseph W; Wang, Xiaopeng; Gallandi, Lukas; Dolgounitcheva, Olga; Ren, Xinguo; Ortiz, J Vincent; Rinke, Patrick; Körzdörfer, Thomas; Marom, Noa

    2016-02-01

    The performance of different GW methods is assessed for a set of 24 organic acceptors. Errors are evaluated with respect to coupled cluster singles, doubles, and perturbative triples [CCSD(T)] reference data for the vertical ionization potentials (IPs) and electron affinities (EAs), extrapolated to the complete basis set limit. Additional comparisons are made to experimental data, where available. We consider fully self-consistent GW (scGW), partial self-consistency in the Green's function (scGW0), non-self-consistent G0W0 based on several mean-field starting points, and a "beyond GW" second-order screened exchange (SOSEX) correction to G0W0. We also describe the implementation of the self-consistent Coulomb hole with screened exchange method (COHSEX), which serves as one of the mean-field starting points. The best performers overall are G0W0+SOSEX and G0W0 based on an IP-tuned long-range corrected hybrid functional with the former being more accurate for EAs and the latter for IPs. Both provide a balanced treatment of localized vs delocalized states and valence spectra in good agreement with photoemission spectroscopy (PES) experiments. PMID:26731609

  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. 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. PMID:26267186

  3. 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.

  4. 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.

  5. Regulated In Situ Generation of Molecular Ions or Protonated Molecules under Atmospheric-Pressure Helium-Plasma-Ionization Mass Spectrometric Conditions

    NASA Astrophysics Data System (ADS)

    Gangam, Rekha; Pavlov, Julius; Attygalle, Athula B.

    2015-07-01

    In an enclosed atmospheric-pressure helium-plasma ionization (HePI) source engulfed with dehumidified ambient gases, molecular cations are generated from compounds such as toluene, bromobenzene, and iodobenzene. Evidently, the ionization is effected by a direct Penning mechanism attributable to interactions of the gas-phase analyte with metastable helium atoms. It is widely known that secondary ions generated from ambient gases also play an important role in the overall ionization process. For example, when the ambient gases bear even traces of moisture, the analytes are ionized by proton transfer reactions with gaseous H3O+. In this study, we demonstrate how a controlled variation of experimental conditions can manipulate the abundance of molecular ions and protonated molecules in a HePI source.

  6. CORRIGENDUM: Corrections to the following three papers pertaining to electron impact ionization efficiency curves calculated using the BEB model for molecules containing third and fourth row atoms

    NASA Astrophysics Data System (ADS)

    Vallance, Claire; Harland, Peter W.

    2005-04-01

    Absolute electron impact ionization cross sections for CH3X, where X = H, F, Cl, Br, and I Claire Vallance et al 1997 J. Phys. B: At. Mol. Opt. Phys. 30 2465 2475 Absolute electron-impact ionization cross sections for a range of C1 to C5 chlorocarbons James E Hudson et al 2001 J. Phys. B: At. Mol. Opt. Phys. 34 3025 3039 Absolute electron impact ionization cross-sections for CO, CO2, OCS and CS2 James E Hudson et al 2004 J. Phys. B: At. Mol. Opt. Phys. 37 445 455 We have recently re-examined some published binary-encounter Bethe (BEB) calculations on the electron impact ionization cross sections for halogenated hydrocarbons and sulfur-containing molecules, and found a discrepancy with our earlier results. Please see the PDF file for full details.

  7. 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.

  8. N1s and O1s double ionization of the NO and N2O molecules

    NASA Astrophysics Data System (ADS)

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

    2014-01-01

    Single-site N1s and O1s double core ionisation of the NO and N2O 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-2) and 1179.4 eV (O1s-2). The corresponding energies obtained for N2O are 896.9 eV (terminal N1s-2), 906.5 eV (central N1s-2), and 1174.1 eV (O1s-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 N2O, associated with the decay of the terminal and central N1s-2 as well as with the O1s-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 × 10-3 for nitrogen at 1100 eV and as 1.3 × 10-3 for oxygen at 1300 eV.

  9. 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.

  10. N1s and O1s double ionization of the NO and N2O molecules.

    PubMed

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

    2014-01-28

    Single-site N1s and O1s double core ionisation of the NO and N2O 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(-2)) and 1179.4 eV (O1s(-2)). The corresponding energies obtained for N2O are 896.9 eV (terminal N1s(-2)), 906.5 eV (central N1s(-2)), and 1174.1 eV (O1s(-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 N2O, associated with the decay of the terminal and central N1s(-2) as well as with the O1s(-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(-3) for nitrogen at 1100 eV and as 1.3 × 10(-3) for oxygen at 1300 eV. PMID:25669525

  11. 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.

  12. 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

  13. Desorption/ionization of acrylamide in aqueous solutions in atmospheric pressure air using a microdischarge with vortex focusing of ions

    NASA Astrophysics Data System (ADS)

    Pervukhin, V. V.; Sheven', D. G.

    2014-09-01

    A method of desorption/ionization in a microdischarge with ion vortex focusing (vortex focusing microdischarge, VFM) is suggested. A glow microdischarge is initiated in an air flow, and resulting ions act on the surface of interest. As a model compound, an aqueous solution of acrylamide is taken. Desorption/ionization taking place under atmospheric pressure is followed by the mass-spectrometric identification of the ions. The operating parameters of the VFM system are studied and optimized. Upon optimization of the system, the detection limit of acrylamide trace amounts in aqueous solutions is determined using the suggested method of desorption/ionization and analyte ion focusing with a vortex (swirling) jet. The acrylamide detection limit is found to be 2 × 10-3 g/L.

  14. 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.

  15. Analysis of the interactions between pentacene film and air molecules by means of Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    De Angelis, F.; Das, G.; Di Fabrizio, E.

    2008-09-01

    We report on the interactions between spin-coated pentacene films and molecules present in air (nitrogen, oxygen, and moisture) studied by means of micro-Raman spectroscopy. We found that while oxygen does not interact with pentacene, water molecules diffuse in the film proportionally to the relative humidity of the ambient, giving rise to an interaction that affects pentacene's optical properties. These findings are fully reversible when dry ambient is restored, and they could be ascribed to the formation of a reversible water-pentacene complex theoretically calculated. This interaction affects a specific pentacene vibration mode that could lead to reversible formation of electron traps involved in the degradation of the electrical performance of pentacene.

  16. 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.

  17. 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. PMID:27075876

  18. 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

    2016-04-01

    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.

  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. Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry using an inorganic particle matrix for small molecule analysis

    PubMed

    Kinumi; Saisu; Takayama; Niwa

    2000-03-01

    Fine metal or metal oxide powder as an alternative to conventional organic matrices in matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOFMS) has been utilized successfully for lower molecular mass analytes, poly(ethylene glycol) 200 (PEG 200) and methyl stearate. Eleven kinds of particle, Al, Mn, Mo, Si, Sn, SnO2, TiO2, W, WO3, Zn and ZnO, were evaluated. The analyte was mixed with a metal or metal oxide powder (inorganic matrix) with particle diameter of tens of micrometers and liquid dispersant, followed by application to the sample target. Using a commercial MALDI-TOFMS instrument equipped with an internal 337 nm pulsed nitrogen laser, the analytes, PEG 200 and methyl stearate, were ionized as the alkali metal ion adducted molecules [M+Na]+ or [M+K]+ when the inorganic matrices Mn, Mo, Si, Sn, TiO2, W, WO3, Zn or ZnO were used. In the case of an Al matrix, PEG 200 was ionized as [M+K]+, whereas methyl stearate was ionized as [M+H]+ and [M+Al]+. These particles have potential as the matrix for MALDI. During our examination, however, only SnO2 particles did not ionize either PEG 200 or methyl stearate. Based on our protocol, when TiO2 powder was suspended with liquid paraffin, PEG 200 and methyl stearate gave their MALDI-TOF mass spectra with the lowest background noise and highest intensity. TiO2 powder seemed to be a broad potential matrix for low molecular mass polar or non-polar analytes. The results suggested that bulk particles caused rapid heating/vaporization processes and ionized analyte molecules under irradiation with a pulsed UV laser. The present method can be readily applied to obtain the low background noise MALDI-TOF mass spectra of small-sized compounds. PMID:10767772

  1. Partial-ionization cross sections of a CO{sub 2} molecule due to impact of 10-26-keV electrons

    SciTech Connect

    Bhatt, Pragya; Singh, Raj; Yadav, Namita; Shanker, R.

    2010-10-15

    Experimental data on total- and partial-ionization cross sections of ionic fragments of CO{sub 2} molecule produced by impact of 10-26-keV electrons are obtained on a crossed-beam apparatus in our laboratory. An ejected electron-produced ion-coincidence technique is employed together with a time-of-flight mass spectrometer for analysis of the ions. The six ionic fragments, CO{sub 2}{sup +}, CO{sup +}, CO{sub 2}{sup 2+}, O{sup +}, C{sup +}, and C{sup 2+}, resulting from dissociative ionization of the CO{sub 2} molecule are observed and identified; their relative ionization cross sections and branching ratios are determined as a function of impact energy. The binary-encounter Bethe model is found to overestimate the experimental data for total-ionization cross sections of the observed ions. No other experimental or theoretical data exist in the investigated energy range to make a direct comparison with the present results.

  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. Precursor ionization ahead of laser-supported detonation wave in air and argon

    NASA Astrophysics Data System (ADS)

    Shimamura, Kohei; Komurasaki, Kimiya; Koizumi, Hiroyuki; Arakawa, Yoshihiro

    2012-10-01

    Laser-produced plasma in a gaseous form is considered, which has attracted great interest for use in many devices. After breakdown one of possible mechanisms of occurrence of this process is noted as laser-supported detonation wave. This wave consisting of the shock wave and the beam absorbing plasma travels at several kilometers per second along the laser beam channel in the direction opposite to the beam incidence. A Nd: Glass laser and a TEA CO2 laser were utilized. According to shadowgraph and spectroscopic studies, the wave has a velocity of 1-10 km/s, an electron temperature of 2-5 eV and an electron density of 10^24 m-3 after breakdown. For simplicity, the discussion is restricted to one-dimensional flows that considers the radiation from plasma and the collisional ionization by laser irradiation. Assuming that UV photons radiating from laser plasma induce photoionization ahead of ionization front, this ionization frequency fp at the distance lp (mean free path of photon) from the wave front corresponds to 10^10 s-1. This is higher than the collisional ionization frequency (10^5-6 s-1). Analytical velocities (fplp) describing the avalanche ionization in the pre-ionization layer agree with the experimentally observed velocities. These results does not depend on background gas and laser-wavelength.

  4. 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 PAGESBeta

    Lopez-Hilfiker, Felipe D.; Iyer, Siddarth; Mohr, Claudia; Lee, Ben H.; D'Ambro, Emma L.; Kurten, 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. Lastly, 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

  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 PAGESBeta

    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. Strong-field approximation for ionization of a diatomic molecule by a strong laser field. II. The role of electron rescattering off the molecular centers

    NASA Astrophysics Data System (ADS)

    Busuladžić, M.; Gazibegović-Busuladžić, A.; Milošević, D. B.; Becker, W.

    2008-09-01

    The strong-field approximation for ionization of diatomic molecules by a strong laser field [D. B. Milošević, Phys. Rev. A 74, 063404 (2006)] is generalized to include rescattering of the ionized electron wave packet off the molecular centers (the electron’s parent ion or the second atom). There are four rescattering contributions to the ionization rate, which are responsible for the high-energy plateau in the electron spectra and which interfere in a complicated manner. The spectra are even more complicated due to the different symmetry properties of the atomic orbitals of which a particular molecular orbital consists. Nevertheless, a comparatively simple condition emerges for the destructive interference of all these contributions, which yields a curve in the (Epf,θ) plane. Here θ is the electron emission angle and Epf is the electron kinetic energy. The resulting suppression of the rescattering plateau can be strong and affect a large area of the (Epf,θ) plane, depending on the orientation of the molecule. We illustrate this using the examples of the 3σg molecular orbital of N2 and the 1πg molecular orbital of O2 for various orientations of these molecules with respect to the laser polarization axis. For N2 , for perpendicular orientation and the equilibrium internuclear distance R0 , we find that the minima of the ionization rate form the curve Epfcos2θ=π2/(2R02) in the (Epf,θ) plane. For O2 the rescattering plateau is absent for perpendicular orientation.

  8. Excitational energy transfer enhancing ionization and spatial-temporal evolution of air breakdown with UV laser radiation

    NASA Astrophysics Data System (ADS)

    Hummelt, Jason S.; Scharer, John E.

    2010-11-01

    This paper examines the role multiphoton excitation of oxygen has on the ionization of nitrogen in laser air breakdown. Plasma is created by focusing a 193 nm ArF excimer laser using an 18 cm focal length lens, producing a cylindrical 540 μm wide spot of intensity 6.5 GW/cm2, well below the classical limit for collisional cascade (CC) breakdown. By spectroscopically monitoring the B Σ2u+ to X Σ2g+ transition at 391.4 nm of N2+ in N2 and O2 mixes, collisions between N2 and metastable O2 states that have undergone 1+1 absorption processes are shown to lower the degree of nonlinearity (i.e., the number of photons involved in the rate limiting multiphoton absorption process) in the ionization of N2. This process is also found to dominate the 2+1 resonant enhanced multiphoton ionization of N2 in air and be the primary source for ionization of N2 to the B Σ2u+ state. Plasma formation and evolution is also examined using a 1.3 cm focal length objective lens creating a 40 μm wide spot of intensity 1.25 TW/cm2, above the classical limit for breakdown. This plasma is imaged with a fast (1.2 ns) gating intensified charge coupled device camera. Early plasma formation is seen to be inhomogeneous in nature, and significant ion density is found to exist up to 20 μs after the laser pulse.

  9. Air- and moisture-stable amphoteric molecules: enabling reagents in synthesis.

    PubMed

    He, Zhi; Zajdlik, Adam; Yudin, Andrei K

    2014-04-15

    Researchers continue to develop chemoselective synthesis strategies with the goal of rapidly assembling complex molecules. As one appealing approach, chemists are searching for new building blocks that include multiple functional groups with orthogonal chemical reactivity. Amphoteric molecules that possess nucleophilic and electrophilic sites offer a versatile platform for the development of chemoselective transformations. As part of a program focused on new methods of synthesis, we have been developing this type of reagents. This Account highlights examples of amphoteric molecules developed by our lab since 2006. We have prepared and evaluated aziridine aldehydes, a class of stable unprotected α-amino aldehydes. Structurally, aziridine aldehydes include both a nucleophilic amine nitrogen and an electrophilic aldehyde carbon over the span of three atoms. Under ambient conditions, these compounds exist as homochiral dimers with an aziridine-fused five-membered cyclic hemiaminal structure. We have investigated chemoselective reactions of aziridine aldehydes that involve both the aziridine and aldehyde functionalities. These transformations have produced a variety of densely functionalized nitrogen-containing compounds, including amino aldehydes, 1,2-diamines, reduced hydantoins, C-vinyl or alkynyl aziridines, and macrocyclic peptides. We have also developed air- and moisture-stable α-boryl aldehydes, another class of molecules that are kinetically amphoteric. The α-boryl aldehydes contain a tetracoordinated N-methyliminodiacetyl (MIDA) boryl substituent, which stabilizes the α-metalloid carbonyl system and prevents isomerization to its O-bond enolate form. Primarily taking advantage of chemoselective transformations at the aldehyde functionality, these α-boryl aldehydes have allowed us to synthesize a series of new functionalized boron-containing compounds that are difficult or impossible to prepare using established protocols, such as α-borylcarboxylic acids

  10. 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

  11. 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.

  12. Low energy ionizing collisions between N2 and CO beam molecules and CO, N2, NO, CH4, and CO2 target molecules

    NASA Technical Reports Server (NTRS)

    Utterback, N. G.; Van Zyl, B.

    1978-01-01

    Absolute total negative charge production cross sections for N2 + CO, CO + N2, CO + CO, N2 + NO, N2 + CH4, and N2 + CO2 collisions are reported, and a simple model of collisions is discussed. The cross sections were measured to within about 1 eV of their thresholds. Specific reaction channels were investigated by referring to mass spectrometric identification of the product ions scattered in the forward direction, and these product ion identifications were used to explain characteristic structures in the total charge production cross sections in the near-threshold regions. The extent of the importance of dissociative ionization and 'simple' ionization in the studied collisions at low energy is considered, and charge transfer cross sections for (CO)+ + CO, CO(+) + CH4, and N2(+) + CH4 are presented.

  13. Effects of the air pressure on the wave-packet dynamics of gaseous iodine molecules at room temperature

    NASA Astrophysics Data System (ADS)

    Fan, Rongwei; He, Ping; Chen, Deying; Xia, Yuanqin; Yu, Xin; Wang, Jialing; Jiang, Yugang

    2013-02-01

    Based on ultrafast laser pulses, time-resolved resonance enhancement coherent anti-Stokes Raman scattering (RE-CARS) is applied to investigate wave-packet dynamics in gaseous iodine. The effects of air pressure on the wave-packet dynamics of iodine molecules are studied at pressures ranging from 1.5 Torr to 750 Torr. The RE-CARS signals are recorded in a gas cell filled with a mixture of about 0.3 Torr iodine in air buffer gas at room temperature. The revivals and fractional revival structures in the wave-packet signal are found to gradually disappear with rising air pressure up to 750 Torr, and the decay behaviors of the excited B-state and ground X-state become faster with increasing air pressure, which is due to the collision effects of the molecules and the growing complexity of the spectra at high pressures.

  14. 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.

  15. Electrosonic spray ionization. A gentle technique for generating folded proteins and protein complexes in the gas phase and for studying ion-molecule reactions at atmospheric pressure.

    PubMed

    Takáts, Zoltán; Wiseman, Justin M; Gologan, Bogdan; Cooks, R Graham

    2004-07-15

    Electrosonic spray ionization (ESSI), a variant on electrospray ionization (ESI), employs a traditional micro ESI source with supersonic nebulizing gas. The high linear velocity of the nebulizing gas provides efficient pneumatic spraying of the charged liquid sample. The variable electrostatic potential can be tuned to allow efficient and gentle ionization. This ionization method is successfully applied to aqueous solutions of various proteins at neutral pH, and its performance is compared to that of the nanospray and micro ESI techniques. Evidence for efficient desolvation during ESSI is provided by the fact that the peak widths for various multiply charged protein ions are an order of magnitude narrower than those for nanospray. Narrow charge-state distributions compared to other ESI techniques are observed also; for most of the proteins studied, more than 90% of the protein ions can be accumulated in one charge state using ESSI when optimizing conditions. The fact that the abundant charge state is normally as low or lower than that recorded by ESI or nanospray indicates that folded protein ions are generated. The sensitivity of the ionization technique to high salt concentrations is comparable to that of nanospray, but ESSI is considerably less sensitive to high concentrations of organic additives such as glycerol or 2-amino-2-(hydroxymethyl)-1,3-propanediol (Tris base). Noncovalent complexes are observed in the case of myoglobin, protein kinase A/ATP complex, and other proteins. The extent of dissociation of protein ions in ESSI is comparable to or even smaller than that in the case of nanospray, emphasizing the gentle nature of the method. The unique features of ESSI are ascribed to very efficient spraying and the low internal energy supplied to the ions. Evidence is provided that the method is capable of generating fully desolvated protein ions at atmospheric pressure. This allows the technique to be used for the study of ion-molecule reactions at atmospheric

  16. 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.

  17. 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

  18. 1,5-Diaminonaphthalene hydrochloride assisted laser desorption/ionization mass spectrometry imaging of small molecules in tissues following focal cerebral ischemia.

    PubMed

    Liu, Huihui; Chen, Rui; Wang, Jiyun; Chen, Suming; Xiong, Caiqiao; Wang, Jianing; Hou, Jian; He, Qing; Zhang, Ning; Nie, Zongxiu; Mao, Lanqun

    2014-10-21

    A sensitive analytical technique for visualizing small endogenous molecules simultaneously is of great significance for clearly elucidating metabolic mechanisms during pathological progression. In the present study, 1,5-naphthalenediamine (1,5-DAN) hydrochloride was prepared for matrix-assisted laser desorption/ionization (MALDI) mass spectrometry imaging (MSI) of small molecules in liver, brain, and kidneys from mice. Furthermore, 1,5-DAN hydrochloride assisted LDI MSI of small molecules in brain tissue of rats subjected to middle cerebral artery occlusion (MCAO) was carried out to investigate the altered metabolic pathways and mechanisms underlying the development of ischemic brain damage. Our results suggested that the newly prepared matrix possessed brilliant features including low cost, strong ultraviolet absorption, high salt tolerance capacity, and fewer background signals especially in the low mass range (typically m/z < 500), which permitted us to visualize the spatial distribution of a broad range of small molecule metabolites including metal ions, amino acids, carboxylic acids, nucleotide derivatives, peptide, and lipids simultaneously. Nineteen endogenous metabolites involved in metabolic networks such as ATP metabolism, tricarboxylic acid (TCA) cycle, glutamate-glutamine cycle, and malate-aspartate shuttle, together with metal ions and phospholipids as well as antioxidants underwent relatively obvious changes after 24 h of MCAO. The results were highly consistent with the data obtained by MRM MS analysis. These findings highlighted the promising potential of the organic salt matrix for application in the field of biomedical research. PMID:25247713

  19. 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.

  20. 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. PMID:27065224

  1. 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.

  2. Late and persistent up-regulation of intercellular adhesion molecule-1 (ICAM-1) expression by ionizing radiation in human endothelial cells in vitro.

    PubMed

    Gaugler, M H; Squiban, C; van der Meeren, A; Bertho, J M; Vandamme, M; Mouthon, M A

    1997-08-01

    Adhesion molecules play a key role in cellular traffic through vascular endothelium, in particular during the inflammatory response when leukocytes migrate from blood into tissues. Since inflammation is one of the major consequences of radiation injury, we investigated the effect of ionizing radiation on cell-surface expression of the intercellular adhesion molecule-1 (ICAM-1), the vascular cell adhesion molecule-1 (VCAM-1) and E-selectin in cultured human umbilical vein endothelial cells (HUVEC). Flow cytometry performed on irradiated HUVEC revealed both a time- (from 2 to 10 days) and dose- (from 2 to 10 Gy) dependent up-regulation of basal expression of ICAM-1, and no induction of VCAM-1 or E-selectin. The radiation-induced increase in ICAM-1 expression on HUVEC was correlated with augmented adhesion of neutrophils on irradiated endothelial cells. Interleukin-6 (Il-6) or other soluble factors released by irradiation were not involved in the enhanced ICAM-1 expression by irradiation. Northern blot analysis showed an overexpression of ICAM-1 mRNA from 1 to 6 days after a 10 Gy exposure. Our data suggest that ICAM-1 participates in the radiation-induced inflammatory reaction of the endothelium. PMID:9269313

  3. 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

  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. 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.

  7. 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.

  8. Effects of molecular rotation after ionization and prior to fragmentation on observed recoil-frame photoelectron angular distributions in the dissociative photoionization of nonlinear molecules

    NASA Astrophysics Data System (ADS)

    López-Domínguez, Jesús A.; Lucchese, Robert R.

    2016-03-01

    Experimental angle-resolved photoelectron-photoion coincidence experiments measure photoelectron angular distributions (PADs) in dissociative photoionization (DPI) in the reference frame provided by the momenta of the emitted heavy fragments. By extension of the nomenclature used with DPI of diatomic molecules, we refer to such a PAD as a recoil-frame PAD (RFPAD). When the dissociation is fast compared to molecular rotational and bending motions, the emission directions of the heavy fragments can be used to determine the orientation of the bonds that are broken in the DPI at the time of the ionization, which is known as the axial-recoil approximation (ARA). When the ARA is valid, the RFPADs correspond to molecular-frame photoelectron angular distributions (MFPADs) when the momenta of a sufficient number of the heavy fragments are determined. When only two fragments are formed, the experiment cannot measure the orientation of the fragments about the recoil axes so that the resulting measured PAD is an azimuthally averaged RFPAD (AA-RFPAD). In this study we consider how the breakdown of the ARA due to rotation will modify the observed RFPADs for DPI processes in nonlinear molecules for ionization by light of arbitrary polarization. This model is applied to the core C 1 s DPI of CH4, with the results compared to experimental measurements and previous theoretical calculations done within the ARA. The published results indicate that there is a breakdown in the ARA for two-fragment events where the heavy-fragment kinetic energy release was less than 9 eV. Including the breakdown of the ARA due to rotation in our calculations gives very good agreement with the experimental AA-RFPAD, leading to an estimate of upper bounds on the predissociative lifetimes as a function of the kinetic energy release of the intermediate ion states formed in the DPI process.

  9. 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. PMID:20806261

  10. Inner-shell ionization of rotating linear molecules in the presence of spin-dependent interactions: Entanglement between a photoelectron and an auger electron

    NASA Astrophysics Data System (ADS)

    Ghosh, R.; Chandra, N.; Parida, S.

    2009-03-01

    This paper reports results of a theoretical study of angle- and spin-resolved photo-Auger electron coincident spectroscopy in the form of entanglement between these two particles emitted from a linear molecule. First, we develop an expression for a density matrix needed for studying spin-entanglement between a photoelectron and an Auger electron. In order to properly represent the molecular symmetries, nuclear rotation, and the spin-dependent interactions (SDIs), we have used symmetry adapted wavefunctions in Hund’s coupling scheme (a) for all the species participating in this two-step process. This expression shows that spin-entanglement in a photo-Auger electron pair in the presence of SDIs very strongly depends upon, among other things, polarization of the ionizing radia- tion, directions of motion and of spin polarization of two ejected electrons, and the dynamics of photoionization and of Auger decay. We have applied this expression, as an example, to a generic linear molecule in its J0, M0 = 0 state. This model calculation clearly brings out the salient features of the spin-entanglement of a photo-Auger electron pair in the presence of the SDIs.

  11. Formation of ultracold (7)Li(85)Rb molecules in the lowest triplet electronic state by photoassociation and their detection by ionization spectroscopy.

    PubMed

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

    2015-03-21

    We report the formation of ultracold (7)Li(85)Rb molecules in the a(3)Σ(+) 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(-1) below the (7)Li 2s (2)S1/2 + (85)Rb 5p (2)P1/2 asymptote. In addition, we use REMPI spectroscopy to probe the a(3)Σ(+) state and excited electronic 3(3)Π and 4(3)Σ(+) states and identify a(3)Σ(+) (v″ = 7-13), 3(3)Π (vΠ' = 0-10), and 4(3)Σ(+) (vΣ' = 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. PMID:25796252

  12. 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.

  13. On the influence of singlet oxygen molecules on the speed of flame propagation in methane-air mixture

    SciTech Connect

    Starik, A.M.; Kozlov, V.E.; Titova, N.S.

    2010-02-15

    The effect of the presence of singlet oxygen molecules O{sub 2}(a{sup 1}{delta}{sub g}) in a CH{sub 4}-air mixture on the speed of laminar flame propagation is considered. The known experimental data on the laminar flame speed and ignition delay are used to validate the developed kinetic model involving electronically excited oxygen molecules O{sub 2}(a{sup 1}{delta}{sub g}) and O{sub 2}(b{sup 1}{sigma}{sub g}{sup +}). Numerical simulation shows that the presence of 10% O{sub 2}(a{sup 1}{delta}{sub g}) in molecular oxygen enables to increase significantly (by a factor of 1.7) the speed of flame propagation in a fuel-lean ({phi}=0.45) methane-air mixture. The main reason for such an acceleration of flame propagation is the intensification of chain reactions due to addition of singlet delta oxygen molecules. For a fuel-rich mixture ({phi}=1.9), the growth in the flame speed is significantly smaller and attains a factor of 1.4. (author)

  14. 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.

  15. 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

  16. 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.

  17. Long-lived Electronic Coherence of Rydberg States in the Strong-Field Ionization of a Polyatomic Molecule

    NASA Astrophysics Data System (ADS)

    Konar, Arkaprabha; Shu, Yinan; Levine, Benjamin; Lozovoy, Vadim; Dantus, Marcos

    2015-05-01

    Here, we report on quantum coherent control of a large (>20 atoms) polyatomic molecule. In particular, we explore the time resolved dynamics of dicyclopentadiene when excited by a pair of phase-locked intense 800nm femtosecond pulses by monitoring changes in ion yield of the parent and fragments. Long-lived oscillations are observed for ~ 500 fs in the parent ion yield indicating the presence of long lived-electronic states. We take advantage of the long-lived electronic coherence to control the yield of different fragment ions. The presence of Rydberg states is further supported by ab initio calculations at the EOM-CCSD/6-31 +G** level of theory which identified five low-lying electronic states of neutral DCPD in the regions between 6.4 and 7.0 eV in vertical excitation energy. States of both pure Rydberg and mixed π --> π */Rydberg character are observed in this low energy region and are known to originate from ethylene. The multiphoton excitation of two or more Rydberg states, separated by the photon energy is the key to the observed long-lived electronic coherence in DCPD with a quantum beat at the difference frequency. Rydberg states are expected to have very similar potential energy surfaces and the Rydberg electron is relatively uncoupled to the nuclear dynamics, therefore supporting long electronic coherence time.

  18. Small molecule GS-nitroxide ameliorates ionizing irradiation-induced delay in bone wound healing in a novel murine model.

    PubMed

    Gokhale, Abhay; Rwigema, Jean-Claude; Epperly, Michael W; Glowacki, Julie; Wang, Hong; Wipf, Peter; Goff, Julie P; Dixon, Tracy; Patrene, Ken; Greenberger, Joel S

    2010-01-01

    We studied radioprotection and mitigation by mitochondrial-targeted Tempol (GS-nitroxide, JP4-039), in a mouse injury/irradiation model of combined injury (fracture/irradiation). Right hind legs of control C57BL/6NHsd female mice, mice pretreated with MnSOD-PL, JP4-039, or with amifostine were irradiated with single and fractionated doses of 0 to 20 Gy. Twenty-four hours later, unicortical holes were drilled into the tibiae of both hind legs; at intervals, tibias were excised, radiographed, and processed for histology. Bone wounds irradiated to 20 or 30 Gy showed delayed healing at 21 to 28 days. Treatment with JP4-039 MnSOD-PL or amifostine, before or after single fraction 20 Gy or during fractionated irradiation followed by drilling accelerated wound healing at days 21 and 28. Orthotopic 3LL tumors were not protected by JP4-039 or amifostine. In nonirradiated mice, pretreatment with JP4-039 accelerated bone wound healing. This test system should be useful for the development of new small molecule radioprotectors. PMID:20668303

  19. 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.

  20. 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.

  1. Real-time air monitoring of mustard gas and Lewisite 1 by detecting their in-line reaction products by atmospheric pressure chemical ionization ion trap tandem mass spectrometry with counterflow ion introduction.

    PubMed

    Okumura, Akihiko; Takada, Yasuaki; Watanabe, Susumu; Hashimoto, Hiroaki; Ezawa, Naoya; Seto, Yasuo; Sekiguchi, Hiroshi; Maruko, Hisashi; Takayama, Yasuo; Sekioka, Ryoji; Yamaguchi, Shintaro; Kishi, Shintaro; Satoh, Takafumi; Kondo, Tomohide; Nagashima, Hisayuki; Nagoya, Tomoki

    2015-01-20

    A new method enabling sensitive real-time air monitoring of highly reactive chemical warfare agents, namely, mustard gas (HD) and Lewisite 1 (L1), by detecting ions of their in-line reaction products instead of intact agents, is proposed. The method is based on corona discharge-initiated atmospheric pressure chemical ionization coupled with ion trap tandem mass spectrometry (MS(n)) via counterflow ion introduction. Therefore, it allows for highly sensitive and specific real-time detection of a broad range of airborne compounds. In-line chemical reactions, ionization reactions, and ion fragmentations of these agents were investigated. Mustard gas is oxygenated in small quantity by reactive oxygen species generated in the corona discharge. With increasing air humidity, the MS(2) signal intensity of protonated molecules of mono-oxygenated HD decreases but exceeds that of dominantly existing intact HD. This result can be explained in view of proton affinity. Lewisite 1 is hydrolyzed and oxidized. As the humidity increases from zero, the signal of the final product, namely, didechlorinated, dihydroxylated, and mono-oxygenated L1, quickly increases and reaches a plateau, giving the highest MS(2) and MS(3) signals among those of L1 and its reaction products. The addition of minimal moisture gives the highest signal intensity, even under low humidity. The method was demonstrated to provide sufficient analytical performance to meet the requirements concerning hygienic management and counter-terrorism. It will be the first practical method, in view of sensitivity and specificity, for real-time air monitoring of HD and L1 without sample pretreatment. PMID:25553788

  2. 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

  3. 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.

  4. 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.

  5. 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 ...

  6. Ozone: An Air Pollutant Acting as a Plant-Signaling Molecule

    NASA Astrophysics Data System (ADS)

    Sandermann, Heinrich, Jr.

    The air pollutant ozone has recently been found to trigger plant signal transduction chains resembling those induced by fungal and viral pathogens. Chloroplast-related functions are generally inhibited, while genes of antioxidative and pathogen defense are activated. The resulting perturbation of plant metabolism leads to higher susceptibility (or in certain cases higher tolerance) for other abiotic and biotic stressors. This mechanism of action links ozone by some criteria to "novel" forest decline and to agricultural crop loss. Further progress appears to depend on coordinated long-term laboratory and field experiments.

  7. Development of a particle-trap preconcentration-soft ionization mass spectrometric technique for the quantification of mercury halides in air.

    PubMed

    Deeds, Daniel A; Ghoshdastidar, Avik; Raofie, Farhad; Guérette, Élise-Andrée; Tessier, Alain; Ariya, Parisa A

    2015-01-01

    Measurement of oxidized mercury, Hg(II), in the atmosphere poses a significant analytical challenge as Hg(II) is present at ultra-trace concentrations (picograms per cubic meter air). Current technologies are sufficiently sensitive to measure the total Hg present as Hg(II) but cannot determine the chemical speciation of Hg(II). We detail here the development of a soft ionization mass spectrometric technique coupled with preconcentration onto nano- or microparticle-based traps prior to analysis for the measurement of mercury halides in air. The current methodology has comparable detection limits (4-11 pg m(-3)) to previously developed techniques for the measurement of total inorganic mercury in air while allowing for the identification of HgX2 in collected samples. Both mercury chloride and mercury bromide have been sporadically detected in Montreal urban and indoor air using atmospheric pressure chemical ionization-mass spectrometry (APCI-MS). We discuss limitations and advantages of the current technique and discuss potential avenues for future research including quantitative trace measurements of a larger range of mercury compounds. PMID:25837315

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

    PubMed

    Gunzer, Frank

    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

  9. 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

  10. 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.

  11. 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

  12. 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.

  13. Ultrafast imaging the light-speed propagation of a focused femtosecond laser pulse in air and its ionized electron dynamics and plasma-induced pulse reshaping

    NASA Astrophysics Data System (ADS)

    Yu, Yanwu; Jiang, Lan; Cao, Qiang; Shi, Xueshong; Wang, Qingsong; Wang, Guoyan; Lu, Yongfeng

    2016-03-01

    The light-speed propagation of a focused femtosecond (fs) laser pulse in air was recorded by a pump-probe shadowgraph imaging technique with femtosecond time resolution. The ultrafast dynamics of the laser-ionized electrons were studied, which revealed a strong reshaping of the laser field due to laser-air nonlinear interaction. The influence of laser fluence and focusing conditions on the pulse reshaping was studied, and it was found that: (1) double foci are formed due to the refocusing effect when the laser fluence is higher than 500 J/cm2 and the focusing numeric aperture (NA) is higher than 0.30; and (2) a higher NA focusing lens can better inhibit the prefocusing effect and nonlinear distortion in the Gaussian beam waist.

  14. Intense laser ionization of transiently aligned CO

    SciTech Connect

    Pinkham, D.; Jones, R.R.

    2005-08-15

    We have measured the ionization rate for CO molecules exposed to intense 30 fsec 780 nm laser pulses as a function of the angle between the molecular and laser polarization axes. Nonionizing, 70 fsec laser pulses are used to coherently prepare the molecules, preferentially aligning them for the strong-field ionization experiments. We find a 2:1 ionization-rate ratio for molecules aligned parallel or perpendicular to the ionizing field.

  15. 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

  16. 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

  17. Hierarchical assembly of an achiral pi-conjugated molecule into a chiral nanotube through the air/water interface.

    PubMed

    Yao, Pingping; Wang, Haifeng; Chen, Penglei; Zhan, Xiaowei; Kuang, Xun; Zhu, Daoben; Liu, Minghua

    2009-06-16

    An achiral pi-conjugated fluorinated fused pyrazine derivative has been spread at the air/water interface, and its assembling property is investigated. It has been found that the compound, although without any long alkyl chain, could be spread as a floating film on water surface, the surface pressure of which can be compressed up to ca. 70 mN/m. An inflection point has been observed in the isotherm of the floating film on water surface. The atomic force microscope (AFM), scanning electron microscope (SEM) as well as the transmission electron microscope (TEM) observations revealed that the floating film first formed a multilayer structure and then was compressed into nanotubes after the inflection region as a result of the rolling of the ultrathin film. Interestingly, the rolled nanotubes show circular dichroism although the molecule itself is an achiral species, suggesting the chiral nanotube is predominantly produced on the water surface. The investigation provides an effective way to fabricate supramolecular-based organic chiral nanotubes through an interfacial supramolecular assembly process. PMID:19459675

  18. 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

  19. 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. PMID:24116663

  20. 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

  1. 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.

    2016-04-01

    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.

  2. 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.

  3. 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.

  4. 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

  5. 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...

  6. 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...

  7. Penning ionization : In benzene · Ar and fluorobenzene · Ar van der waals molecules and in collisions of benzene with metastable Ar atoms

    NASA Astrophysics Data System (ADS)

    Rühl, E.; Bisling, P.; Brutschy, B.; Beckmann, K.; Leisen, O.; Morgner, H.

    1986-08-01

    The photoion efficiency curves of the van der Waals complexes benzene ·Ar (Bz·Ar) and fluorobenzene·Ar (Fb·Ar) exhibit sharp resonances, which correspond to excitation to the Ar 2P 3/24s and 2P 1/24s resonance states. The peaks are redshifted relative to their asymptotic values (Bz·Ar, Δ E = -70 ± 10 meV; Fb·Ar, Δ E = -40 ± 10 meV). These findings are supported by electron spectroscopy studies of the Penning ionization of benzene by state-selected metastable Ar ( 3p 2, 3p 0) atoms. Strong evidence is presented that Penning ionization is the process observed in both cases.

  8. 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

  9. Femtosecond Laser Ionization of Organic Amines with Very Low Ionization Potential.

    NASA Astrophysics Data System (ADS)

    Yatsuhashi, Tomoyuki; Obayashi, Takashi; Tanaka, Michinori; Murakami, Masanao; Nakashima, Nobuaki

    2006-03-01

    The interaction between high intensity femtosecond laser and molecules is one of the most attractive areas in laser chemistry and ionization is the most fundamental subject. Theoretical consideration successfully reproduced the ionization behavior of rare gases. However, the understanding of ionization mechanisms of large molecules is difficult more than those of rare gases due to their complexity. Generally speaking, molecules are harder to ionize than rare gases even if they have the same ionization potential. The suppressed ionization phenomena are one of the important features of molecular ionization. Hankin et al. examined 23 organic molecules with ionization potentials between 8.25 and 11.52 eV. We have examined ionization and/ or fragmentation of many organic molecules, including aromatic compounds, halogenated compounds, methane derivatives etc. at various wavelengths below 10^16 Wcm-2. In order to investigate the nature of molecular ionization, it is interesting to examine a variety of molecule in a wide range of ionization potential. In this study, we examined several organic amines because we can explore the uninvestigated ionization potential range down to 5.95 eV. In addition to the significant suppression of the ionization rates, stepwise ionization behavior, which was not observed in rare gases, was observed.

  10. 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.

  11. A first-principle protocol for calculating ionization energies and redox potentials of solvated molecules and ions: Theory and application to aqueous phenol and phenolate

    PubMed Central

    Ghosh, Debashree; Roy, Anirban; Seidel, Robert; Winter, Bernd; Bradforth, Stephen; Krylov, Anna I.

    2012-01-01

    The effect of hydration on the lowest vertical ionization energy (VIE) of phenol and phenolate solvated in bulk water was characterized using the equation-of-motion ionization potential coupled-cluster (EOM-IP-CCSD) and effective fragment potential (EFP) methods (referred to as EOM/EFP), and determined experimentally by valence photo-emission measurements using microjets and synchrotron radiation. The computed solvent-induced shifts in VIEs (ΔVIE) are −0.66 eV and +5.72 eV for phenol and phenolate, respectively. Our best estimates of the absolute values of VIEs (7.9 and 7.7 eV for phenol and phenolate) agree reasonably well with the respective experimental values (7.8±0.1 eV and 7.1±0.1 eV). The EOM/EFP scheme was benchmarked against full EOM-IP-CCSD using micro-solvated phenol and phenolate clusters. A protocol for calculating redox potentials with EOM/EFP was developed based on linear response approximation (LRA) of free energy determination. The oxidation potentials of phenol and phenolate calculated using LRA and EOM/EFP are 1.32 V and 0.89 V, respectively; they agree well with experimental values. PMID:22497288

  12. Kinetic-energy release in the dissociative capture-ionization of CO molecules by 97-MeV Ar14+ ions

    NASA Astrophysics Data System (ADS)

    Watson, R. L.; Sampoll, G.; Horvat, V.; Heber, O.

    1996-02-01

    The dissociation of COQ+ molecular ions (Q=4 to 9) produced in multiply ionizing collisions accompanied by the transfer of an electron to the projectile has been studied using time-of-flight techniques. Analysis of the coincident-ion-pair flight-time-difference distributions yielded average values of the kinetic-energy releases for the various dissociation reactions. These values were found to be as much as a factor of 2 greater than the kinetic-energy releases expected for dissociation along Coulombic potential curves. The average kinetic-energy release observed for a given ion pair with charges q1 and q2 are nearly equal to the point-charge Coulomb potential energies for an ion pair with charges q1+1 and q2+1, suggesting that the parent molecular ion is formed with two electrons, on average, in highly excited states that do not contribute to the screening of the nuclei.

  13. A fitting formula for radiative cooling based on non-local thermodynamic equilibrium population from weakly-ionized air plasma

    NASA Astrophysics Data System (ADS)

    Ogino, Yousuke; Nagano, Atsushi; Ishihara, Tomoaki; Ohnishi, Naofumi

    2013-08-01

    A fitting formula for radiative cooling with collisional-radiative population for air plasma flowfield has been developed. Population number densities are calculated from rate equations in order to evaluate the effects of nonequilibrium atomic and molecular processes. Many elementary processes are integrated to be applied to optically-thin plasmas in the number density range of 1012/cm3 <= N <= 1019/cm3 and the temperature range of 300 K <= T <= 40,000 K. Our results of the total radiative emissivity calculated from the collisional-radiative population are fitted in terms of temperature and total number density. To validate the analytic fitting formula, numerical simulation of a laser-induced blast wave propagation with the nonequilibrium radiative cooling is conducted and successfully reproduces the shock and plasma wave front time history observed by experiments. In addition, from the comparison between numerical simulations with the radiation cooling effect based on the fitting formula and those with a gray gas radiation model that assumes local thermodynamic equilibrium, we find that the displacement of the plasma front is slightly different due to the deviation of population probabilities. By using the fitting formula, we can easily and more accurately evaluate the radiative cooling effect without solving detailed collisional-radiative rate equations.

  14. 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.

  15. Determination of triazole pesticide residues in edible oils using air-assisted liquid-liquid microextraction followed by gas chromatography with flame ionization detection.

    PubMed

    Farajzadeh, Mir Ali; Feriduni, Behruz; Mogaddam, Mohammad Reza Afshar

    2015-03-01

    In the present study, a rapid, simple, and highly efficient sample preparation method based on air-assisted liquid-liquid microextraction followed by gas chromatography with flame ionization detection was developed for the extraction, preconcentration, and determination of five triazole pesticides (penconazole, hexaconazole, diniconazole, tebuconazole, and triticonazole) in edible oils. Initially, the oil samples were diluted with hexane and a few microliter of a less soluble organic solvent (extraction solvent) in hexane was added. To form fine and dispersed extraction solvent droplets, the mixture of oil sample solution and extraction solvent is repeatedly aspirated and dispersed with a syringe. Under the optimum extraction conditions, the method showed low limits of detection and quantification between 2.2-6.1 and 7.3-20 μg/L, respectively. Enrichment factors and extraction recoveries were in the ranges of 71-96 and 71-96%, respectively. The relative standard deviations for the extraction of 100 and 250 μg/L of each pesticide were less than 5% for intraday (n = 6) and interday (n = 3) precisions. Finally edible oil samples were successfully analyzed using the proposed method, and hexaconazole was found in grape seed oil. PMID:25580590

  16. Calcium - ionized

    MedlinePlus

    ... at both ionized calcium and calcium attached to proteins. You may need to have a separate ionized calcium test if you have factors that increase or decrease total calcium levels. These may include abnormal blood levels ...

  17. 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

  18. 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

  19. The Zebrafish- Danio rerio – Is a Useful Model for Measuring the Effects of Small-molecule Mitigators of Late Effects of Ionizing Irradiation

    PubMed Central

    EPPERLY, MICHAEL W.; BAHARY, NATHAN; QUADER, MUBINA; DEWALD, VALERIE; GREENBERGER, JOEL S.

    2013-01-01

    Background/Aim Use of zebrafish models may decrease the cost of screening new irradiation protectors and mitigators. Materials and Methods Zebrafish (Danio rerio) models were tested for screening water-soluble radiation protectors and mitigators. Irradiation of embryos and monitoring survival, and measuring fibrosis of the caudal musculature of adults allowed for testing of acute and late effects, respectively. Results Incubation of zebrafish embryos either before or after irradiation in ethyl pyruvate (1 mM) increased survival. Irradiation of adults to 15 to 75 Gy, delivered in single-fraction at 13 Gy/min, showed dose-dependent fibrosis at 30 days, quantitated as physiological decrease in swimming tail movement, and histopathological detection of collagen deposition in the dorsal musculature. Continuous administration of small-molecule radioprotector drugs in the water after irradiation reduced both acute and chronic injuries. Conclusion The zebrafish is cost-effective for screening new radiation countermeasures. PMID:23160669

  20. "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.

  1. "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

  2. Remote mass spectrometric sampling of electrospray- and desorption electrospray-generated ions using an air ejector.

    PubMed

    Dixon, R Brent; Bereman, Michael S; Muddiman, David C; Hawkridge, Adam M

    2007-10-01

    A commercial air ejector was coupled to an electrospray ionization linear ion trap mass spectrometer (LTQ) to transport remotely generated ions from both electrospray (ESI) and desorption electrospray ionization (DESI) sources. We demonstrate the remote analysis of a series of analyte ions that range from small molecules and polymers to polypeptides using the AE-LTQ interface. The details of the ESI-AE-LTQ and DESI-AE-LTQ experimental configurations are described and preliminary mass spectrometric data are presented. PMID:17716909

  3. Remote Mass Spectrometric Sampling of Electrospray- and Desorption Electrospray-Generated Ions Using an Air Ejector

    PubMed Central

    Dixon, R. Brent; Bereman, Michael S.; Muddiman, David C.; Hawkridge, Adam M.

    2007-01-01

    A commercial air ejector was coupled to an electrospray ionization linear ion trap mass spectrometer (LTQ) to transport remotely generated ions from both electrospray (ESI) and desorption electrospray ionization (DESI) sources. We demonstrate the remote analysis of a series of analyte ions that range from small molecules and polymers to polypeptides using the AE-LTQ interface. The details of the ESI-AE-LTQ and DESI-AE-LTQ experimental configurations are described and preliminary mass spectrometric data is presented. PMID:17716909

  4. 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.

  5. Ionizing radiation

    Technology Transfer Automated Retrieval System (TEKTRAN)

    This chapter gives a comprehensive review on ionizing irradiation of fresh fruits and vegetables. Topics include principles of ionizing radiation, its effects on pathogenic and spoilage microorganisms, shelf-life, sensory quality, nutritional and phytochemical composition, as well as physiologic and...

  6. 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.

  7. 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.

  8. Correlation of ionizing irradiation-induced late pulmonary fibrosis with long-term bone marrow culture fibroblast progenitor cell biology in mice homozygous deletion recombinant negative for endothelial cell adhesion molecules.

    PubMed

    Epperly, Michael W; Guo, Hongliang; Shields, Donna; Zhang, Xichen; Greenberger, Joel S

    2004-01-01

    Ionizing irradiation damage to the lung is associated with an acute inflammatory reaction, followed by a latent period and then late effects including predominantly pulmonary fibrosis. The cells mediating fibrosis have recently been shown to derive from the bone marrow hematopoietic microenvironment. Initiation of late pulmonary irradiation lung damage has been correlated with up-regulation of VCAM-1 and ICAM-1 in pulmonary endothelial cells, followed by infiltration of macrophages and bone marrow-derived fibroblasts forming the fibrotic lesions of organizing alveolitis/fibrosis. To determine whether the absence of expression of VCAM-1, ICAM-1, or other adhesion molecules known to be relevant to inflammatory cell attachment to lung endothelial cells was associated with a decrease in irradiation-induced lung fibrosis, homozygous deletion recombinant knockout mice lacking each of several adhesion molecules were tested compared to littermates for survival and development of organizing alveolitis following 20 Gy irradiation to both lungs. Bone marrow culture longevity has been shown to be a parameter, which correlates with both hematopoietic stem cell reserve and the integrity of fibroblast progenitors of the supportive hematopoietic microenvironment; radiation lung survival data were correlated to longevity of hematopoiesis in long-term bone marrow cultures established from tibia and femur bone marrow of the same mice. Homozygous deletion recombinant negative mice including VCAM-1-/-, ICAM-1-/-, E-Selectin-/-, or L-Selectin-/- were irradiated to 20 Gy to both lungs and followed for survival and percent organizing alveolitis at time of death compared to each normal littermate. A significant increase in survival (median 190 days) was detected with L-Selectin-/- compared to littermate control mice (median 140 days) or other groups. Long-term bone marrow cultures from L-Selectin-/- mice showed no detectable difference in marrow fibroblasts or hematopoietic cell biology

  9. 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 %. PMID:26994011

  10. Ultraviolet femtosecond laser ionization mass spectrometry.

    PubMed

    Imasaka, Totaro

    2008-01-01

    For this study, multiphoton ionization/mass spectrometry using an ultraviolet (UV) femtosecond laser was employed for the trace analysis of organic compounds. Some of the molecules, such as dioxins, contain several chlorine atoms and have short excited-state lifetimes due to a "heavy atom" effect. A UV femtosecond laser is, then, useful for efficient resonance excitation and subsequent ionization. A technique of multiphoton ionization using an extremely short laser pulse (e.g., <10 fs), referred to as "impulsive ionization," may have a potential for use in fragmentation-free ionization, thus providing information on molecular weight in mass spectrometry. PMID:18302290

  11. 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.

  12. 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. PMID:24725876

  13. 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

  14. Ultrasensitive detection of atmospheric constituents by supersonic molecular beam, multiphoton ionization, mass spectroscopy.

    PubMed

    Syage, J A; Pollard, J E; Cohen, R B

    1987-09-01

    An ultrasensitive detection method for atmospheric monitoring has been developed based on the technique of supersonic molecular beam, resonance enhanced multiphoton ionization, and time-of-flight mass spectroscopy (MB/REMPI/TOFMS). Several organophosphonate and organosulfide compounds, representing simulants to a class of toxic compounds, were studied. Detection levels as low as 300 ppt (dimethyl sulfide) were obtained. Single-vibronic-level REMPI of the cooled molecules in conjunction with TOFMS provided selectivity of ~10(4) against chemically similar compounds in humid air expansions. The fragment ions formed by REMPI excitation are shown for diisopropyl methylphosphonate to depend strongly on the resonant intermediate state of the neutral molecule. PMID:20490096

  15. 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. PMID:24377283

  16. 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.

  17. 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.

  18. 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.

  19. 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.

  20. 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

  1. Multiphoton ionization of N2 by the third harmonic of a Nd:YAG laser - A new avenue for air diagnostics

    NASA Technical Reports Server (NTRS)

    Laufer, Gabriel; Krauss, Roland H.; Grinstead, Jay H.

    1991-01-01

    Laser-induced N2 ionization is accomplished using a commercially available Nd:YAG laser, and confirmed by means of ion-collection and spectral measurements. Neutral N2 is excited by six photons of the third harmonic frequency, or 355 nm, and is transformed to an ionized state. The radiation at 355 nm is separated from the fundamental and frequency-doubled Nd:YAG radiation to guarantee monochromatic incident radiation. Intense lines near 391.4 nm are found in the initial laser polarization and for a 90-degree rotation of polarization. The radiation at 391.4 nm is associated with an incoherent laser-induced flourescence process related to an ionized-state transition, and increases quadratically with laser power. A 45-mJ laser pulse focused to a diameter of 17 microns can produce an ion concentration of 3.25 x 10 to the 13th ions/cu cm. The large ion concentration and robust fluorescence signal make this technique an efficient method for time-of-flight velocimetry and in-flight testing.

  2. Ultratrace detection of chemical warfare agent simulants using supersonic-molecular-beam, resonance-enhanced multiphoton-ionization, time-of-flight mass spectroscopy. Final report

    SciTech Connect

    Syage, J.A.; Pollard, J.E.; Cohen, R.B.

    1988-02-15

    An ultratrace detection method that offers exceptional selectivity has been developed based on the technique of supersonic molecular beam, resonance enhanced multiphoton ionization, time-of-flight mass spectroscopy (MB/REMPI/TOFMS). Single ion detection capability has given detection limits as low as 300 ppt (dimethyl sulfide). Single vibronic level REMPI of the supercooled molecules in conjunction with TOFMS provides selectivity of 10,000 against chemically similar compounds. Studies were carried out using moist air expansions for a variety of organophosphonate and sulfide chemical warfare agent (CWA) simulant molecules. The preparation of molecules in single vibronic levels by laser excitation in supersonic molecular beams has enabled us to record high resolution spectra of higher excited electronic states showing fully resolved vibrational structure for diisopropyl methylphosphonate (DIMP) and dimethyl sulfide (DMS). VUV absorption spectra have also been recorded for several CWA molecules at ambient temperature, revealing several new electronic states extending up to the ionization threshold.

  3. Ambient aerodynamic ionization source for remote analyte sampling and mass spectrometric analysis.

    PubMed

    Dixon, R Brent; Sampson, Jason S; Hawkridge, Adam M; Muddiman, David C

    2008-07-01

    The use of aerodynamic devices in ambient ionization source development has become increasingly prevalent in the field of mass spectrometry. In this study, an air ejector has been constructed from inexpensive, commercially available components to incorporate an electrospray ionization emitter within the exhaust jet of the device. This novel aerodynamic device, herein termed remote analyte sampling, transport, and ionization relay (RASTIR) was used to remotely sample neutral species in the ambient and entrain them into an electrospray plume where they were subsequently ionized and detected using a linear ion trap Fourier transform mass spectrometer. Two sets of experiments were performed in the ambient environment to demonstrate the device's utility. The first involved the remote (approximately 1 ft) vacuum collection of pure sample particulates (i.e., dry powder) from a glass slide, entrainment and ionization at the ESI emitter, and mass spectrometric detection. The second experiment involved the capture (vacuum collection) of matrix-assisted laser desorbed proteins followed by entrainment in the ESI emitter plume, multiple charging, and mass spectrometric detection. This approach is in principle a RASTIR-assisted matrix-assisted laser desorption electrospray ionization source (Sampson, J. S.; Hawkridge, A. M.; Muddiman, D. C. J. Am. Soc. Mass Spectrom. 2006, 17, 1712-1716; Rapid Commun. Mass Spectrom. 2007, 21, 1150-1154.). A detailed description of the device construction, operational parameters, and preliminary small molecule and protein data are presented. PMID:18529018

  4. 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.

  5. 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+.

  6. 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

  7. 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

    2016-04-01

    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+.

  8. INSTRUMENTS AND METHODS OF INVESTIGATION: Surface-ionization field mass-spectrometry studies of nonequilibrium surface ionization

    NASA Astrophysics Data System (ADS)

    Blashenkov, Nikolai M.; Lavrent'ev, Gennadii Ya

    2007-01-01

    The ionization of polyatomic molecules on tungsten and tungsten oxide surfaces is considered for quasiequilibrium or essentially nonequilibrium conditions (in the latter case, the term nonequilibrium surface ionization is used for adsorbate ionization). Heterogeneous reactions are supposed to proceed through monomolecular decay of polyatomic molecules or fragments of multimolecular complexes. The nonequilibrium nature of these reactions is established. The dependences of the current density of disordered ions on the surface temperature, electric field strength, and ionized particle energy distribution are obtained in analytical form. Heterogeneous dissociation energies, the ionization potentials of radicals, and the magnitude of reaction departure from equilibrium are determined from experimental data, as are energy exchange times between reaction products and surfaces, the number of molecules in molecular complexes, and the number of effective degrees of freedom in molecules and complexes. In collecting the data a new technique relying on surface-ionization field mass-spectrometry was applied.

  9. New standards for ionizing radiation measurements

    SciTech Connect

    Lamperti, P.J.; Johnson, C.M.

    1995-12-31

    The Ionizing Radiation Division has developed new national standards for mammographic X rays and for brachytherapy sources, such as iodine-125. The Attix chamber, a variable volume free-air ionization chamber, has been established as the primary national standard for mammographic X rays. The Attix chamber resides in the newly developed NIST Mammography Calibration Range and will be used to perform routine calibrations. The wide-angle free-air ionization chamber utilizes a large volume and a novel electric field configuration in order to circumvent the limitations of conventional free-air chambers. Seventeen beam qualities for X rays from molybdenum (Mo) and rhodium (Rh) anodes have been parameterized for the calibration of mammographic ionization chambers. The beam qualities available include anode/filter combinations of Mo/Mo, Mo/Rh and Rh/Rh. The mammography range was developed in collaborations with the U.S. Food and Drug Administration`s (FDA) Center for Devices and Radiological Health, the implementors of the Mammography Quality Standards Act (MQSA) of 1992. The wide-angle free-air ionization chamber has been used to measure the output of two types of iodine-125 seeds, those with resin balls and those with silver wire. Both free-air chambers have been intercompared with the Ritz parallel-plate free-air ionization chamber.

  10. 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. PMID:24588987

  11. 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.

  12. 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.

  13. 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.

  14. 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.

    PubMed

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

    2012-09-14

    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 N(2)(+)(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 N(2)(+)(X (2)Σ(g)(+), 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 N(2)(+) PFI-PI beam can be formed with a laboratory kinetic energy resolution of ΔE(lab) = ± 50 meV. As a result, the total cross section measurement can be conducted at center-of-mass kinetic energies (E(cm)'s) down to thermal energies. Absolute total rovibrationally selected cross sections σ(v(+) = 0-2, N(+) = 0-9) for the N(2)(+)(X (2)Σ(g)(+); v(+) = 0-2, N(+) = 0-9) + Ar CT reaction have been measured in the E(cm) range of 0.04-10.0 eV, revealing strong vibrational enhancements and E(cm)-dependencies of σ(v(+) = 0-2, N(+) = 0-9). The thermochemical threshold at E(cm) = 0.179 eV for the formation of Ar(+) from N(2)(+)(X; v(+) = 0, N(+)) + Ar was observed by the measured σ(v(+) = 0), confirming the narrow ΔE(cm) 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

  15. 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.

  16. An atmospheric pressure chemical ionization study of the positive and negative ion chemistry of the hydrofluorocarbons 1,1-difluoroethane (HFC-152a) and 1,1,1,2-tetrafluoroethane (HFC-134a) and of perfluoro-n-hexane (FC-72) in air plasma at atmospheric pressure.

    PubMed

    Marotta, Ester; Paradisi, Cristina; Scorrano, Gianfranco

    2004-07-01

    A report is given on the ionization/dissociation behavior of the title compounds within air plasmas produced by electrical corona discharges at atmospheric pressure: both positive and negative ions were investigated at different temperatures using atmospheric pressure chemical ionization mass spectrometry (APCI-MS). CHF(2)CH(3) (HFC-152a) undergoes efficient ionic oxidation to C(2)H(5)O(+), in which the oxygen comes from water present in the plasma. In contrast, CF(3)CH(2)F (HFC-134a) does not produce any characteristic positive ion under APCI conditions, its presence within the plasma being revealed only as a neutral ligand in ion-molecule complexes with ions of the background (H(3)O(+) and NO(+)). Analogously, the perfluorocarbon FC-72 (n-C(6)F(14)) does not produce significant positive ions at 30 degrees C: at high temperature, however, it undergoes dissociative ionization to form many product ions including C(3)F(6)(+), C(2)F(4)(+), C(n)F(2n+1)(+) and a few families of oxygen containing cations (C(n)F(2n+1)OH(2)(+), C(n)F(2n)OH(+), C(n)F(2n-1)O(+), C(n)F(2n-1)O(2)H(2)(+), C(n)F(2n-2)O(2)H(+)) which are suggested to derive from C(n)F(2n+1)(+) in a cascade of steps initiated by condensation with water followed by steps of HF elimination and H(2)O addition. Negative ions formed from the fluoroethanes CHF(2)CH(3) and CF(3)CH(2)F (M) include complexes with ions of the background, O(2)(-)(M), O(3)(-)(M) and some higher complexes involving also water, and complexes of the fluoride ion, F(-)(H(2)O), F(-)(M) and higher complexes with both M and H(2)O also together. The interesting product O(2)(-)(HF) is also formed from 1,1-difluoroethane. In contrast to the HFCs, perfluoro-n-hexane gives stable molecular anions, M(-), which at low source temperature or in humidified air are also detected as hydrates, M(-)(H(2)O). In addition, in humidified air F(-)(H(2)O)(n) complexes are also formed. The reactions leading to all major positive and negative product ions are discussed

  17. Electron impact ionization and multiphoton ionization of doped superfluid helium droplets: A comparison

    NASA Astrophysics Data System (ADS)

    He, Yunteng; Zhang, Jie; Kong, Wei

    2016-02-01

    We compare characteristics of electron impact ionization (EI) and multiphoton ionization (MPI) of doped superfluid helium droplets using the same droplet source. Selected dopant ion fragments from the two ionization schemes demonstrate different dependence on the doping pressure, which could be attributed to the different ionization mechanisms. While EI directly ionizes helium atoms in a droplet therefore has higher yields for bigger droplets (within a limited size range), MPI is insensitive to the helium in a droplet and is only dependent on the number of dopant molecules. The optimal timing of the ionization pulse also varies with the doping pressure, implying a velocity slip among different sized droplets. Calculations of the doping statistics and ionization probabilities qualitatively agree with the experimental data. Our results offer a word of caution in interpreting the pressure and timing dependence of superfluid helium droplets, and we also devise a scheme in achieving a high degree of doping while limiting the contribution of dopant clusters.

  18. Electron impact ionization and multiphoton ionization of doped superfluid helium droplets: A comparison.

    PubMed

    He, Yunteng; Zhang, Jie; Kong, Wei

    2016-02-28

    We compare characteristics of electron impact ionization (EI) and multiphoton ionization (MPI) of doped superfluid helium droplets using the same droplet source. Selected dopant ion fragments from the two ionization schemes demonstrate different dependence on the doping pressure, which could be attributed to the different ionization mechanisms. While EI directly ionizes helium atoms in a droplet therefore has higher yields for bigger droplets (within a limited size range), MPI is insensitive to the helium in a droplet and is only dependent on the number of dopant molecules. The optimal timing of the ionization pulse also varies with the doping pressure, implying a velocity slip among different sized droplets. Calculations of the doping statistics and ionization probabilities qualitatively agree with the experimental data. Our results offer a word of caution in interpreting the pressure and timing dependence of superfluid helium droplets, and we also devise a scheme in achieving a high degree of doping while limiting the contribution of dopant clusters. PMID:26931697

  19. Method and apparatus to monitor a beam of ionizing radiation

    SciTech Connect

    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.

  20. 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

  1. 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

  2. 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.

  3. Model CRAC:EPII for atmospheric ionization due to precipitating electrons: Yield function and applications

    NASA Astrophysics Data System (ADS)

    Artamonov, A. A.; Mishev, A. L.; Usoskin, I. G.

    2016-02-01

    A new model of the family of CRAC models, CRAC:EPII (Cosmic Ray Atmospheric Cascade: Electron Precipitation Induced Ionization), is presented. The model calculates atmospheric ionization induced by precipitating electrons and uses the formalism of ionization yield functions. The CRAC:EPII model is based on a full Monte Carlo simulation of electron propagation and interaction with the air molecules. It explicitly considers various physical processes, namely, pair production, Compton scattering, generation of bremsstrahlung high-energy photons, photoionization, annihilation of positrons, and multiple scattering. The simulations were performed using GEANT 4 simulation tool PLANETOCOSMICS with NRLMSISE 00 atmospheric model. The CRAC:EPII model is applicable to the entire atmosphere. The results from the simulations are given as look-up table representing the ionization yield function. The table allows one to compute ionization due to precipitating electrons for a given altitude and location considering a given electron spectrum. Application of the model for computation of ion production during electron precipitation events using spectra from balloon-borne measurements is presented.

  4. [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. PMID:25055654

  5. 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.

  6. 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.

  7. 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. PMID:26496892

  8. Poster — Thur Eve — 24: Commissioning and preliminary measurements using an Attix-style free air ionization chamber for air kerma measurements on the BioMedical Imaging and Therapy beamlines at the Canadian Light Source

    SciTech Connect

    Anderson, D; McEwen, M; Shen, H; Siegbahn, EA; Fallone, BG; Warkentin, B

    2014-08-15

    Synchrotron facilities, including the Canadian Light Source (CLS), provide opportunities for the development of novel imaging and therapy applications. A vital step progressing these applications toward clinical trials is the availability of accurate dosimetry. In this study, a refurbished Attix-style (cylindrical) free air chamber (FAC) is tested and used for preliminary air kerma measurements on the two BioMedical Imaging and Therapy (BMIT) beamlines at the CLS. The FAC consists of a telescoping chamber that relies on a difference measurement of collected charge in expanded and collapsed configurations. At the National Research Council's X-ray facility, a Victoreen Model 480 FAC was benchmarked against two primary standard FACs. The results indicated an absolute accuracy at the 0.5% level for energies between 60 and 150 kVp. A series of measurements were conducted on the small, non-uniform X-ray beams of the 05B1-1 (∼8 – 100 keV) and 05ID-2 (∼20 – 200 keV) beamlines for a variety of energies, filtrations and beam sizes. For the 05B1-1 beam with 1.1 mm of Cu filtration, recombination corrections of less than 5 % could only be achieved for field sizes no greater than 0.5 mm × 0.6 mm (corresponding to an air kerma rate of ∼ 57 Gy/min). Ionic recombination thus presents a significant challenge to obtaining accurate air kerma rate measurements using this FAC in these high intensity beams. Future work includes measurements using a smaller aperture to sample a smaller and thus more uniform beam area, as well as experimental and Monte Carlo-based investigation of correction factors.

  9. 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.

  10. 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.

  11. Establishing Atmospheric Pressure Chemical Ionization Efficiency Scale.

    PubMed

    Rebane, Riin; Kruve, Anneli; Liigand, Piia; Liigand, Jaanus; Herodes, Koit; Leito, Ivo

    2016-04-01

    Recent evidence has shown that the atmospheric pressure chemical ionization (APCI) mechanism can be more complex than generally assumed. In order to better understand the processes in the APCI source, for the first time, an ionization efficiency scale for an APCI source has been created. The scale spans over 5 logIE (were IE is ionization efficiency) units and includes 40 compounds with a wide range of chemical and physical properties. The results of the experiments show that for most of the compounds the ionization efficiency order in the APCI source is surprisingly similar to that in the ESI source. Most of the compounds that are best ionized in the APCI source are not small volatile molecules. Large tetraalkylammonium cations are a prominent example. At the same time, low-polarity hydrocarbons pyrene and anthracene are ionized in the APCI source but not in the ESI source. These results strongly imply that in APCI several ionization mechanisms operate in parallel and a mechanism not relying on evaporation of neutral molecules from droplets has significantly higher influence than commonly assumed. PMID:26943482

  12. 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

  13. Weakly ionized cosmic gas: Ionization and characterization

    NASA Technical Reports Server (NTRS)

    Rosenberg, M.; Mendis, D. A.; Chow, V. W.

    1994-01-01

    Since collective plasma behavior may determine important transport processes (e.g., plasma diffusion across a magnetic field) in certain cosmic environments, it is important to delineate the parameter space in which weakly ionized cosmic gases may be characterized as plasmas. In this short note, we do so. First, we use values for the ionization fraction given in the literature, wherein the ionization is generally assumed to be due primarily to ionization by cosmic rays. We also discuss an additional mechanism for ionization in such environments, namely, the photoelectric emission of electrons from cosmic dust grains in an interstellar Far Ultra Violet (FUV) radiation field. Simple estimates suggest that under certain conditions this mechanism may dominate cosmic ray ionization, and possibly also the photoionization of metal atoms by the interstellar FUV field, and thereby lead to an enhanced ionization level.

  14. 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

  15. Molecular Double Ionization Using Strong Field Few-Cycle Laser Pulses.

    PubMed

    Zhao, Arthur; Sándor, Péter; Tagliamonti, Vincent; Matsika, Spiridoula; Weinacht, Thomas

    2016-05-19

    We study strong field double ionization of a series of organic molecules by making use of coincidence detection of fragment ions. We measure the double ionization yield as a function of pulse duration, intensity, polarization, and molecular conjugation. For conjugated molecules we find strong enhancement in the double ionization rate over what one would expect on the basis of tunneling or multiphoton ionization rates. Calculations reveal a correlation between the electronic structure of the different molecules and the observed double ionization yields, highlighting the removal of electrons from inner orbitals. PMID:26927812

  16. Compact Raman Lidar Measurement of Liquid and Vapor Phase Water Under the Influence of Ionizing Radiation

    NASA Astrophysics Data System (ADS)

    Shiina, Tatsuo; Chigira, Tomoyuki; Saito, Hayato; Manago, Naohiro; Kuze, Hiroaki; Hanyu, Toshinori; Kanayama, Fumihiko; Fukushima, Mineo

    2016-06-01

    A compact Raman lidar has been developed for studying phase changes of water in the atmosphere under the influence of ionization radiation. The Raman lidar is operated at the wavelength of 349 nm and backscattered Raman signals of liquid and vapor phase water are detected at 396 and 400 nm, respectively. Alpha particles emitted from 241Am of 9 MBq ionize air molecules in a scattering chamber, and the resulting ions lead to the formation of liquid water droplets. From the analysis of Raman signal intensities, it has been found that the increase in the liquid water Raman channel is approximately 3 times as much as the decrease in the vapor phase water Raman channel, which is consistent with the theoretical prediction based on the Raman cross-sections. In addition, the radius of the water droplet is estimated to be 0.2 μm.

  17. 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.

  18. Thermochromic behaviors and ionization potentials of organopolysilanes

    NASA Astrophysics Data System (ADS)

    Yokoyama, Kenji; Yokoyama, Masaaki

    1989-04-01

    Ionization potentials of organopolysilanes with different kinds of substituents were evaluated from the low energy photo-electron emission measurements in air. An aryl-substituted organopolysilane capable of σ - π mixing between Si backbone σ and side-group π electrons gave smaller ionization potential by about 0.1˜0.15 eV compared with alkyl-substituted organopolysilanes. The value of ionization potentials in some alkyl-substituted organopolysilanes which showed thermochromic behaviors was found to vary substantially with thermally induced reversible changes in polymer backbone conformation, indicating that the effective conjugation length of σ electrons decreases above the thermochromic transition temperature.

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

    SciTech Connect

    Bhatt, Pragya; Singh, Raj; Yadav, Namita; Shanker, R.

    2011-10-15

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

  20. 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.

  1. 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.

  2. 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)

  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. Fragmentation pathways of ethylene after core ionization

    NASA Astrophysics Data System (ADS)

    Gaire, B.; Bocharova, I.; Sturm, F. P.; Gehrken, N.; Haxton, D. J.; Belkacem, A.; Weber, Th.; Zohrabi, M.; Ben-Itzhak, I.; Gatton, A.; Williams, J.; Reedy, D.; Nook, C.; Landers, A.; Gassert, H.; Zeller, S.; Voigtsberger, J.; Jahnke, T.; Doerner, R.

    2014-05-01

    We have measured the Auger electrons in coincidence with the recoil ions, resulting from the core ionization of ethylene molecules, by employing the COLd Target Recoil Ion Momentum Spectroscopy (COLTRIMS) method. The Auger-electron and recoil-ion energy maps are used to identify the fragmentation pathways and they are compared to the valence photo-double-ionization of ethylene. The dicationic electronic states favored by the propensity rules are identified and their role on the fragmentation pathways is discussed. The molecular-frame Auger electron angular distribution provides further insight into the breakup of this molecule after core ionization. Supported by the Director, Office of Science, Office of Basic Energy Sciences, and by the Division of Chemical Sciences, Geosciences, and Biosciences of the U.S. Department of Energy at LBNL under Contract No. DE-AC02-05CH11231.

  6. 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

  7. 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

  8. 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.

  9. 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.

  10. Attosecond time-delay spectroscopy of the hydrogen molecule

    NASA Astrophysics Data System (ADS)

    Ivanov, I. A.; Kheifets, A. S.; Serov, Vladislav V.

    2012-12-01

    We apply the concept of photoemission time delay to the process of single-photon one-electron ionization of the H2 molecule. We demonstrate that, by resolving the photoelectron detection in time on the attosecond scale, one can extract differential photoionization cross sections for particular field and molecule orientations from the measurement on a randomly oriented molecule

  11. 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…

  12. 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.

  13. Strong field ionization rates simulated with time-dependent configuration interaction and an absorbing potential

    SciTech Connect

    Krause, Pascal; Sonk, Jason A.; Schlegel, H. Bernhard

    2014-05-07

    Ionization rates of molecules have been modeled with time-dependent configuration interaction simulations using atom centered basis sets and a complex absorbing potential. The simulations agree with accurate grid-based calculations for the ionization of hydrogen atom as a function of field strength and for charge resonance enhanced ionization of H{sub 2}{sup +} as the bond is elongated. Unlike grid-based methods, the present approach can be applied to simulate electron dynamics and ionization in multi-electron polyatomic molecules. Calculations on HCl{sup +} and HCO{sup +} demonstrate that these systems also show charge resonance enhanced ionization as the bonds are stretched.

  14. Ambient Ionization Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Huang, Min-Zong; Yuan, Cheng-Hui; Cheng, Sy-Chyi; Cho, Yi-Tzu; Shiea, Jentaie

    2010-07-01

    Mass spectrometric ionization methods that operate under ambient conditions and require minimal or no sample pretreatment have attracted much attention in such fields as biomedicine, food safety, antiterrorism, pharmaceuticals, and environmental pollution. These technologies usually involve separate ionization and sample-introduction events, allowing independent control over each set of conditions. Ionization is typically performed under ambient conditions through use of existing electrospray ionization (ESI) or atmospheric pressure chemical ionization (APCI) techniques. Rapid analyses of gas, liquid, and solid samples are possible with the adoption of various sample-introduction methods. This review sorts different ambient ionization techniques into two main subcategories, primarily on the basis of the ionization processes, that are further differentiated in terms of the approach used for sampling.

  15. Physics of Partially Ionized Plasmas

    NASA Astrophysics Data System (ADS)

    Krishan, Vinod

    2016-05-01

    Figures; Preface; 1. Partially ionized plasmas here and everywhere; 2. Multifluid description of partially ionized plasmas; 3. Equilibrium of partially ionized plasmas; 4. Waves in partially ionized plasmas; 5. Advanced topics in partially ionized plasmas; 6. Research problems in partially ionized plasmas; Supplementary matter; Index.

  16. Modeling of associative ionization reactions in hypersonic rarefied flows

    NASA Astrophysics Data System (ADS)

    Boyd, Iain D.

    2007-09-01

    When vehicles reenter the Earth's atmosphere from space, the hypersonic conditions are sufficiently energetic to generate ionizing reactions. The production of a thin plasma layer around a hypersonic vehicle can block radio waves sent to and from the vehicle, leading to communications blackout. For Earth entry from orbit, the maximum energy involved in molecular collisions requires only associative ionization of air-species to be considered. In the present study, the modeling of such reactions is considered in detail using the direct simulation Monte Carlo (DSMC) method. For typical Earth entry conditions, with a velocity near 8km/s, it is shown that the average ionizing reaction probabilities are small. Special numerical techniques must therefore be used in the DSMC technique in order to numerically resolve these reactions. Additional simulation problems arise from the relatively small mass of the electrons in comparison to the other atoms and molecules in these flow fields. Artificially increasing the electron mass greatly increases computational efficiency, and the viability of this approach is investigated. Simulation results are presented for conditions corresponding to the RAM-C II hypersonic flight experiment that gathered measurements of electron number density. It is demonstrated that simulation results for electron number density in this energy regime are relatively insensitive to the mass of the electrons. Direct comparison of DSMC results with the RAM-C II measurements for electron number density shows excellent agreement. These satisfactory comparisons represent the first direct verification of the ability of the DSMC technique to successfully predict the weak plasma generated around a hypersonic vehicle.

  17. Photofragmentation of a DNA nucleoside thymidine; valence- vs. core ionization

    NASA Astrophysics Data System (ADS)

    Itälä, E.; Kooser, K.; Hägerth, T.; Rachlew, E.; Huels, M. A.; Kukk, E.

    2012-11-01

    The photofragmentation of free thymidine molecule has been studied using combined electron- and ion spectroscopy. The results show that valence- and core ionization processes produce very different fragmentation patterns and that regardless of the photon energy, the photoionization leads almost always to dissociation of the thymidine molecule.

  18. 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.

  19. 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.

  20. Vibrational overtone spectroscopy of H/sub 2/O (4. gamma. /sub OH/) using energy-selective electron impact ionization

    SciTech Connect

    Hayden, C.C.; Penn, S.M.; Carlson, K.J.; Crim, F.F.

    1988-03-24

    The authors describe a new method for obtaining vibrational overtone spectra of polyatomic molecules in supersonic expansions that uses low-energy electrons to ionize the vibrationally excited molecules. Measuring the excitation spectrum of water in the region of the third overtone of the OH stretching vibration (4..sigma../sub OH/) demonstrates the technique. The ionization process is probably not direct but may occur by electron impact excitation to vibrationally and electronically excited states from which the neutral molecule is subsequently ionizes

  1. Interactions between Rydberg atoms and ultracold polar molecules

    NASA Astrophysics Data System (ADS)

    Jayaseelan, Maitreyi; Haruza, Marek; Bigelow, Nicholas P.

    2015-05-01

    We investigate dipolar interactions arising in a hybrid system containing both ultracold polar molecules and atomic Rydberg states. Ultracold NaCs molecules are produced by photoassociation from laser cooled mixtures of sodium and cesium atoms and detected through resonant multi-photon ionization (REMPI). Rydberg atoms with large dipole moments are excited in the atomic cloud using a multi-photon process and detected via field-ionization. We look for evidence of the interactions in the observed spectra.

  2. 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.

  3. Soft Landing of Complex Molecules on Surfaces

    SciTech Connect

    Johnson, Grant E.; Hu, Qichi; Laskin, Julia

    2011-07-01

    Mass spectrometry is a versatile technique for identification and structural characterization of large molecules. The advent of soft ionization techniques such as electrospray (ESI) (1-2) has enabled ionization of a wide variety of complex molecules without significant \\fragmentation while non-thermal ion sources such as laser vaporization (3-4) and magnetron sputtering (5-6) have provided access to materials that cannot, currently, be produced through conventional techniques. Most mass spectrometry studies rely on ionization of a molecule of interest or a complex mixture followed by mass analysis. Alternatively, mass spectrometry may be used as a preparatory technique, in which mass-selected ions are deposited onto solid supports or into liquid materials (7-18). Preparatory mass spectrometry offers several unique advantages for deposition of complex molecules on substrates including the ability to generate high-purity uniform films (19-20), unprecedented selectivity and specificity of preparation of deposited species (11, 21-22), the ability to focus and pattern an ion beam (23-24), and flexibility in both ion formation (1, 3, 25-26) and mass selection (27-32) processes. This review will highlight applications of mass-selected deposition of complex molecules for selective immobilization of biological molecules and catalytically active complexes on substrates.

  4. Fundamental studies and applications of strong field ionization

    NASA Astrophysics Data System (ADS)

    Yan, Lu

    In an intense laser field, atoms and molecules experience tunneling ionization directly to the continuum. We used this method to study several aspects and applications of strong field ionization (SFI) in atoms and molecules. One study used SFI to probe the photofragments produced by photodissociation using DC sliced imaging. The photodissociation mechanism of two polyatomic molecules (sulfur dioxide and nitromethane) were investigated. In a second study, we show the strong field ionization rate depends on the sign of the magnetic number distribution. We detect the signal of sequential double ionization of argon dications by a pump-probe method to investigate the ionization rate sensitivity to circularly polarized light. In a third study, we also found that the modest fragmentation that accompanies strong field ionization may be used to identify isomers and molecules in a complex mixture based on their mass spectral "finger print". The experiments were carried out in a DC sliced imaging apparatus. For the isomer selective detection experiment, the machine was used simply as a time-of-flight mass spectrometer. The mass spectrum of each isomer was used as "basis function" to characterize the complex mixtures quantitatively.

  5. 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

  6. Multiphoton ionization of uranium hexafluoride

    NASA Astrophysics Data System (ADS)

    Armstrong, D. P.; Harkins, D. A.; Compton, R. N.; Ding, D.

    1994-01-01

    Multiphoton ionization (MPI) time-of-flight mass spectroscopy (TOFMS) and photoelectron spectroscopy (PES) studies of UF6 are reported using focused light from the Nd:YAG laser fundamental (λ=1064 nm) and its harmonics (λ=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+x fragment ions, even at the lowest laser power densities at which signal could be detected. In general, the doubly charged uranium ion (U2+) intensity is much greater than that of the singly charged uranium ion (U+). For the case of the tunable dye laser experiments, the Un+ (n=1-4) wavelength dependence is relatively unstructured and does not show observable resonance enhancement at known atomic uranium excitation wavelengths. The MPI-PES studies reveal only very slow electrons (≤0.5 eV) for all wavelengths investigated. The dominance of the U2+ ion, the absence or very small intensities of UF+x (x=1-3) fragments, the unstructured wavelength dependence, and the preponderance of slow electrons all indicate that mechanisms may exist other than ionization of bare U atoms following the stepwise photodissociation of F atoms from the parent molecule. The data also argue against stepwise photodissociation of UF+x (x=5,6) ions. Neither of the traditional MPI mechanisms (``neutral ladder'' or the ``ionic ladder'') are believed to adequately describe the ionization phenomena observed. We propose that the multiphoton excitation of UF6 under these experimental conditions results in a highly excited molecule, superexcited UF6**. The excitation of highly excited UF6** is proposed to be facilitated by the well known ``giant resonance,'' whose energy level lies in the range of 12-14 eV above that of ground state UF6. The highly excited molecule then primarily dissociates, via multiple channels, into Un+, UF+x, fluorine atoms, and ``slow'' electrons, although dissociation

  7. Atmospheric pressure ionization LC-MS-MS determination of urushiol congeners.

    PubMed

    Draper, William M; Wijekoon, Donald; McKinney, Michael; Behniwal, Paramjit; Perera, S Kusum; Flessel, C Peter

    2002-03-27

    This paper describes atmospheric pressure ionization (API) LC-MS-MS determination of urushiols, 3-n-alkenyl- and -alkyl-substituted catechols responsible for poison oak dermatitis. Urushiol was isolated from Western poison oak according to the method of Elsohly et al. (1) (J. Nat. Prod. 1982, 45, 532-538)-the purified preparation contained C(17)- and C(15)-substituted urushiols with zero, one, two, and three double bonds as determined from GC-MS analysis of trimethylsilyl derivatives. Urushiol mixtures were separated on a C(18) reversed phase HPLC column with a methanol-water gradient with urushiols eluting in 100% methanol. Atmospheric pressure chemical ionization (APCI) produced primarily [M - H](-) and MH(+) molecule ions. Electrospray ionization (ESI) yielded [M - H](-) and adduct ions including [M + Cl](-). Daughter ions of [M - H](-) included quinoid radical anions ([M - H - H(2)](-) and m/z 122(-)) and a benzofuran phenate (m/z 135(-)). A suite of hydrocarbon fragments were produced by collision-induced dissociation of MH(+) directly or via an intermediate [MH - H(2)O](+) daughter ion. Six urushiol congeners, one not previously reported in poison oak, were determined by negative ion API-LC-MS-MS with detection limits of approximately 8 pg/microL (ESI) and approximately 800 pg/microL (APCI). API-LC-MS-MS was used to determine urushiol in surface wipes, air samples, and plant materials. PMID:11902923

  8. 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

  9. Structure parameters in molecular tunneling ionization theory

    NASA Astrophysics Data System (ADS)

    Wang, Jun-Ping; Li, Wei; Zhao, Song-Feng

    2014-04-01

    We extracted the accurate structure parameters in molecular tunneling ionization theory (so called MO-ADK theory) for 22 selected linear molecules including some inner orbitals. The molecular wave functions with the correct asymptotic behavior are obtained by solving the time-independent Schrödinger equation with B-spline functions and molecular potentials numerically constructed using the modified Leeuwen-Baerends (LBα) model.

  10. Effects of higher-order Kerr nonlinearity and plasma diffraction on multiple filamentation of ultrashort laser pulses in air

    SciTech Connect

    Huang, T. W.; Zhou, C. T.; Zhang, H.; He, X. T.

    2013-07-15

    The effect of higher-order Kerr nonlinearity on channel formation by, and filamentation of, ultrashort laser pulses propagating in air is considered. Filament patterns originating from multiphoton ionization of the air molecules with and without the higher-order Kerr and molecular-rotation effects are investigated. It is found that diverging multiple filaments are formed if only the plasma-induced defocusing effect is included. In the presence of the higher-order Kerr effects, the light channel can exist for a long distance. The effect of noise on the filament patterns is also discussed.

  11. Effects of higher-order Kerr nonlinearity and plasma diffraction on multiple filamentation of ultrashort laser pulses in air

    NASA Astrophysics Data System (ADS)

    Huang, T. W.; Zhou, C. T.; Zhang, H.; He, X. T.

    2013-07-01

    The effect of higher-order Kerr nonlinearity on channel formation by, and filamentation of, ultrashort laser pulses propagating in air is considered. Filament patterns originating from multiphoton ionization of the air molecules with and without the higher-order Kerr and molecular-rotation effects are investigated. It is found that diverging multiple filaments are formed if only the plasma-induced defocusing effect is included. In the presence of the higher-order Kerr effects, the light channel can exist for a long distance. The effect of noise on the filament patterns is also discussed.

  12. 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.

  13. Soft x-ray ionization induced fragmentation of glycine

    NASA Astrophysics Data System (ADS)

    Itälä, E.; Kooser, K.; Rachlew, E.; Huels, M. A.; Kukk, E.

    2014-06-01

    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-Cα bond and the presence of the CNH_2^+ fragment.

  14. 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

  15. 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.

  16. 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.

  17. 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.

  18. 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

  19. Orbital-resolved strong-field single ionization of acetylene

    NASA Astrophysics Data System (ADS)

    Ji, Qinying; Cui, Sen; You, Xinyuan; Gong, Xiaochun; Song, Qiying; Lin, Kang; Pan, Haifeng; Ding, Jingxin; Zeng, Heping; He, Feng; Wu, Jian

    2015-10-01

    We resolve the strong-field single ionization of acetylene into different channels by differentially normalizing the lateral momenta of the directly escaped electrons from the aligned and antialigned molecules. Distinct electron momentum distributions for different channels are observed using both near-infrared and ultraviolet femtosecond laser pulses with Keldysh parameters close to 1. The results are interpreted as a signature of multiple ionization orbitals.

  20. Mind Molecules

    PubMed Central

    Snyder, Solomon H.

    2011-01-01

    Scientific styles vary tremendously. For me, research is largely about the unfettered pursuit of novel ideas and experiments that can test multiple ideas in a day, not a year, an approach that I learned from my mentor Julius “Julie” Axelrod. This focus on creative conceptualizations has been my métier since working in the summers during medical school at the National Institutes of Health, during my two years in the Axelrod laboratory, and throughout my forty-five years at Johns Hopkins University School of Medicine. Equally important has been the “high” that emerges from brainstorming with my students. Nothing can compare with the eureka moments when, together, we sense new insights and, better yet, when high-risk, high-payoff experiments succeed. Although I have studied many different questions over the years, a common theme emerges: simple biochemical approaches to understanding molecular messengers, usually small molecules. Equally important has been identifying, purifying, and cloning the messengers' relevant biosynthetic, degradative, or target proteins, at all times seeking potential therapeutic relevance in the form of drugs. In the interests of brevity, this Reflections article is highly selective, and, with a few exceptions, literature citations are only of findings of our laboratory that illustrate notable themes. PMID:21543333

  1. 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.

  2. Dielectric barrier discharge ionization for liquid chromatography/mass spectrometry.

    PubMed

    Hayen, Heiko; Michels, Antje; Franzke, Joachim

    2009-12-15

    An atmospheric pressure microplasma ionization source based on a dielectric barrier discharge with a helium plasma cone outside the electrode region has been developed for liquid chromatography/mass spectrometry (LC/MS). For this purpose, the plasma was realized in a commercial atmospheric pressure ionization source. Dielectric barrier discharge ionization (DBDI) was compared to conventional electrospray ionization (ESI), atmospheric pressure chemical ionization (APCI), and atmospheric pressure photoionization (APPI) in the positive ionization mode. Therefore, a heterogeneous compound library was investigated that covered polar compounds such as amino acids, water-soluble vitamins, and nonpolar compounds like polycyclic aromatic hydrocarbons and functionalized hydrocarbons. It turned out that DBDI can be regarded as a soft ionization technique characterized by only minor fragmentation similar to APCI. Mainly protonated molecules were detected. Additionally, molecular ions were observed for polycyclic aromatic hydrocarbons and derivatives thereof. During DBDI, adduct formation with acetonitrile occurred. For aromatic compounds, addition of one to four oxygen atoms and to a smaller extend one nitrogen and oxygen was observed which delivered insight into the complexity of the ionization processes. In general, compounds covering a wider range of polarities can be ionized by DBDI than by ESI. Furthermore, limits of detection compared to APCI are in most cases equal or even better. PMID:19911793

  3. 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.

  4. Analytical model for calibrating laser intensity in strong-field-ionization experiments

    NASA Astrophysics Data System (ADS)

    Zhao, Song-Feng; Le, Anh-Thu; Jin, Cheng; Wang, Xu; Lin, C. D.

    2016-02-01

    The interaction of an intense laser pulse with atoms and molecules depends extremely nonlinearly on the laser intensity. Yet experimentally there still exists no simple reliable methods for determining the peak laser intensity within the focused volume. Here we present a simple method, based on an improved Perelomov-Popov-Terent'ev model, that would allow the calibration of laser intensities from the measured ionization signals of atoms or molecules. The model is first examined by comparing ionization probabilities (or signals) of atoms and several simple diatomic molecules with those from solving the time-dependent Schrödinger equation. We then show the possibility of using this method to calibrate laser intensities for atoms, diatomic molecules as well as large polyatomic molecules, for laser intensities from the multiphoton ionization to tunneling ionization regimes.

  5. Field-free molecular alignment for measuring ionization probability

    NASA Astrophysics Data System (ADS)

    Loriot, V.; Hertz, E.; Lavorel, B.; Faucher, O.

    2008-01-01

    We have shown in a recent letter (Loriot et al 2006 Opt. Lett. 31 2897) the possibility of determining the ionization probability of linear molecules by using an all-optical technique that takes advantage of post-pulse molecular alignment. To that end, we have implemented a 'cross-defocusing' technique producing a signal sensitive to both alignment and ionization. The analysis of the signal provides a quantitative measurement of the ionization probability calibrated with molecular alignment. In the present work, the method is discussed in more detail and applied to the measurement of the ionization probability of N2 as well as to the determination of the ionization ratio between (i) N2 and Ar and (ii) O2 and Xe. We demonstrate in addition a progress in the scheme in order to improve the accuracy at low intensity.

  6. Antioxidant Approaches to Management of Ionizing Irradiation Injury

    PubMed Central

    Greenberger, Joel; Kagan, Valerian; Bayir, Hulya; Wipf, Peter; Epperly, Michael

    2015-01-01

    Ionizing irradiation induces acute and chronic injury to tissues and organs. Applications of antioxidant therapies for the management of ionizing irradiation injury fall into three categories: (1) radiation counter measures against total or partial body irradiation; (2) normal tissue protection against acute organ specific ionizing irradiation injury; and (3) prevention of chronic/late radiation tissue and organ injury. The development of antioxidant therapies to ameliorate ionizing irradiation injury began with initial studies on gene therapy using Manganese Superoxide Dismutase (MnSOD) transgene approaches and evolved into applications of small molecule radiation protectors and mitigators. The understanding of the multiple steps in ionizing radiation-induced cellular, tissue, and organ injury, as well as total body effects is required to optimize the use of antioxidant therapies, and to sequence such approaches with targeted therapies for the multiple steps in the irradiation damage response. PMID:26785339

  7. Antioxidant Approaches to Management of Ionizing Irradiation Injury.

    PubMed

    Greenberger, Joel; Kagan, Valerian; Bayir, Hulya; Wipf, Peter; Epperly, Michael

    2015-01-01

    Ionizing irradiation induces acute and chronic injury to tissues and organs. Applications of antioxidant therapies for the management of ionizing irradiation injury fall into three categories: (1) radiation counter measures against total or partial body irradiation; (2) normal tissue protection against acute organ specific ionizing irradiation injury; and (3) prevention of chronic/late radiation tissue and organ injury. The development of antioxidant therapies to ameliorate ionizing irradiation injury began with initial studies on gene therapy using Manganese Superoxide Dismutase (MnSOD) transgene approaches and evolved into applications of small molecule radiation protectors and mitigators. The understanding of the multiple steps in ionizing radiation-induced cellular, tissue, and organ injury, as well as total body effects is required to optimize the use of antioxidant therapies, and to sequence such approaches with targeted therapies for the multiple steps in the irradiation damage response. PMID:26785339

  8. 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.

  9. Detecting individual atoms and molecules with lasers

    SciTech Connect

    Letokhov, V.S.

    1988-09-01

    Resonance-ionization spectroscopy was developed by the author and his colleagues at the U.S.S.R. Academy of Sciences and, independently, by G. Samuel Husrst and his colleagues at the Oak Ridge National Laboratory. Resonance-ionization spectroscopy relies on lasers. Lasers having a set of chosen wavelengths can be exploited to detect a desired atom or molecule in a mixture. The wavelengths can be tuned to resonate with a set of characteristic wavelengths of the atom or molecule in such a way that the light ionized the atom or the molecule. Once ionized the atom or the molecular fragments will have a net electric charge and can be separated from the mixture by applying an electric field. The sensitivity of the technique suggests an entire range of applications. Investigators might explore the properties of short-lived radioactive nuclei. Or they could detect trace levels of impurities in otherwise pure elements. In practice a solitary rare atom in a sample containing as many as 10 to the 20th atoms of other elements has been registered. 8 figs.

  10. 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.

  11. 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.

  12. 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.

  13. 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.

  14. High Harmonic Generation from Rotationally Excited Molecules

    NASA Astrophysics Data System (ADS)

    Lock, Robynne M.

    2011-12-01

    High harmonic generation (HHG) is understood through a three-step model. A strong laser field ionizes an atom or molecule. The free electron propagates in the laser field and may recombine with the atom or molecule leading to the generation of extreme ultraviolet or soft x-ray light at odd harmonics of the fundamental. Since the wavelength of the recombining electron is on the order of internuclear distances in molecules, HHG acts as a probe of molecular structure and dynamics. Conversely, control of the molecules leads to control of the properties (intensity, phase, and polarization) of the harmonic emission. Rotationally exciting molecules provides field-free molecular alignment at time intervals corresponding to fractions of the rotational period of the molecule. Alignment is necessary for understanding how the harmonic emission depends on molecular structure and alignment. Additionally, HHG acts as a probe of the rotational wavepackets. This thesis reports three experiments on HHG from rotationally excited molecules. Before we can use HHG as a probe of complex molecular dynamics or control harmonic properties through molecules, the harmonic emission from aligned, linear molecules must first be understood. To that end, the first experiment measures the intensity and phase of harmonics generated from N 2O and N2 near times of strong alignment revealing interferences during recombination. The second experiment demonstrates HHG as a sensitive probe of rotational wavepacket dynamics in CO2 and N2O, revealing new revival features not detected by any other probe. The final experiment focuses on understanding and controlling the polarization state of the harmonic emission. Generating elliptically polarized harmonics would be very useful for probing molecular and materials systems. We observe an elliptical dichroism in polarization-resolved measurements of the harmonic emission from aligned N2 and CO2 molecules, revealing evidence for electron-hole dynamics between the

  15. 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.

  16. Dynamic Reactive Ionization with Cluster Secondary Ion Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Tian, Hua; Wucher, Andreas; Winograd, Nicholas

    2016-02-01

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

  17. Air nonlinear dynamics initiated by ultra-intense lambda-cubic terahertz pulses

    NASA Astrophysics Data System (ADS)

    Shalaby, Mostafa; Hauri, Christoph P.

    2015-05-01

    We report on the measurement of the instantaneous Kerr nonlinearity and the retarded alignment of air molecules CO2, N2, and O2 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.

  18. 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.

  19. 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.

  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 Ionization Measurements

    NASA Astrophysics Data System (ADS)

    Slack, Thomas; Mayes, Riley

    2015-04-01

    The measurement of atmospheric ionization is a largely unexplored science that potentially holds the key to better understanding many different geophysical phenomena through this new and valuable source of data. Through the LaACES program, which is funded by NASA through the Louisiana Space Consortium, students at Loyola University New Orleans have pursued the goal of measuring high altitude ionization for nearly three years, and were the first to successfully collect ionization data at altitudes over 30,000 feet using a scientific weather balloon flown from the NASA Columbia Scientific Ballooning Facility in Palestine, TX. In order to measure atmospheric ionization, the science team uses a lightweight and highly customized sensor known as a Gerdien condenser. Among other branches of science the data is already being used for, such as the study of aerosol pollution levels in the atmosphere, the data may also be useful in meteorology and seismology. Ionization data might provide another variable with which to predict weather or seismic activity more accurately and further in advance. Thomas Slack and Riley Mayes have served as project managers for the experiment, and have extensive knowledge of the experiment from the ground up. LaSPACE Louisiana Space Consortium.

  2. 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.

  3. [Structural anomalies of dog hemoglobin after ionizing irradiation].

    PubMed

    Sukhomlinov, B F; Savich, A V; Shal'no, M I; Starikovich, L S; Dudok, E P

    1981-01-01

    Heterogeneity of dog hemoglobin is established with application of chromatographic analysis. Ionizing radiation (4 Grey) induces no changes in the ratio of hemoglobin components. The comparative dactylographical analysis of the hemoglobin components in norm and in different periods after irradiation revealed differences in responses to tryptophan in peptide T-25. The changes found are connected with disturbances in the structure of the DNA molecule as well as with modification of the protein molecule under conditions of radiation injury. PMID:7324186

  4. ESTIMATION OF IONIZATION CONSTANTS OF AZO DYES AND RELATED AROMATIC AMINES: ENVIRONMENTAL IMPLICATIONS

    EPA Science Inventory

    Ionization constants for 214 dye molecules were calculated from molecular structures using the chemical reactivity models developed in SPARC (SPARC Performs Automated Reasoning in Chemistry). hese models used fundamental chemical structure theory to predict chemical reactivities ...

  5. Inner-shell and double ionization potentials of aminophenol isomers.

    SciTech Connect

    Kryzhevoi, N. V.; Santra, R.; Cederbaum, L. S.

    2011-01-01

    A comprehensive study of single and double core ionization potentials of the aminophenol molecule is reported. The role of relaxation, correlation, relativistic, and basis set effects in these potentials is clarified. Special attention is paid to the isomer dependence of the single and double core ionization potentials. Some of them are also compared with the respective values of the phenol and aniline molecules. It is shown that the core level single ionization potentials of the para-, meta-, and ortho-aminophenol molecules differ only slightly from each other, rendering these structural isomers challenging to distinguish for conventional x-ray photoelectron spectroscopy. In contrast, the energy needed to remove two core electrons from different atoms depends noticeably on the mutual arrangement and even on the relative orientations of the hydroxyl and amine groups. Together with the electrostatic repulsion between the two core holes, relaxation effects accompanying double core ionization play a crucial role here. The pronounced sensitivity of the double ionization potentials, therefore, enables a spectroscopic characterization of the electronic structure of aminophenol isomers by means of x-ray two-photon photoelectron spectroscopy.

  6. 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.

  7. 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

  8. 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.

  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. 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.

  11. Hydrocarbon rate coefficients for proton and electron impact ionization, dissociation, and recombination in a hydrogen plasma.

    SciTech Connect

    Alman, D.A.; Brooks, J.N.; Ruzic, D.N.; Wang, Z.

    1999-07-21

    We estimate cross sections and rate coefficients for proton and electron impact ionization, dissociation, and recombination of neutral and ionized hydrocarbon molecules and fragments of the form C{sub x}H{sub y}{sup k}, x = 1-3, y = 1-6, k = 0,1 in a thermalized hydrogen-electron plasma.

  12. Large molecules in diffuse interstellar clouds

    SciTech Connect

    Lepp, S.; Dalgarno, A.; Van Dishoeck, E.F.; Black, J.H.

    1988-06-01

    The effects of the presence of a substantial component of large molecules on the chemistry of diffuse molecular clouds are explored, and detailed models of the zeta Persei and zeta Ophiuchi clouds are constructed. The major consequence is a reduction in the abundances of singly charged atomic species. The long-standing discrepancy between cloud densities inferred from rotational and fine-structure level populations and from the ionization balance can be resolved by postulating a fractional abundance of large molecules of 1 x 10 to the -7th for zeta Persei and 6 x 10 to the -7th for zeta Ophiuchi. If the large molecules are polycyclic aromatic hydrocarbons (PAH) containing about 50 carbon atoms, they contain 1 percent of the carbon in zeta Persei and 7 percent in zeta Ophiuchi. Other consequences of the possible presence of PAH molecules are discussed. 23 references.

  13. Probing the mechanisms of an air amplifier using a LTQ-FT-ICR-MS and fluorescence spectroscopy.

    PubMed

    Dixon, R Brent; Muddiman, David C; Hawkridge, Adam M; Fedorov, A G

    2007-11-01

    We report the first quantitative assessment of electrosprayed droplet/ion focusing enabled by the use of a voltage-assisted air amplifier between an electrospray ionization emitter and a hybrid linear ion trap Fourier transform ion cyclotron resonance mass spectrometer (ESI-LTQ-FT-ICR-MS). A solution of fluorescent dye was electrosprayed with a stainless steel mesh screen placed in front of the MS inlet capillary acting as a gas-permeable imaging plate for fluorescence spectroscopy. Without use of the air amplifier, no detectable FT-ICR signal was observed, as well as no detectable fluorescence on the screen upon imaging using a fluorescence scanner. When the air amplifier was turned ON while electrospraying the fluorescent dye, FT-ICR mass spectra with high signal to noise ratio were obtained with an average ion injection time of 21 ms for an AGC target value of 5 x 10(5). Imaging of the screen using a fluorescence scanner produced a distinct spot of cross-sectional area approximately 33.5 mm(2) in front of the MS inlet capillary. These experimental results provide direct evidence of aerodynamic focusing of electrosprayed droplets/ions enabled by an air amplifier, resulting in improved electrospray droplet/ion capture efficiency and reduced ion injection time. A second set of experiments was carried out to explore whether the air amplifier assists in desolvation. By electrospraying a mix of quaternary amines, ratios of increasingly hydrophobic molecules were obtained. Observation of the solvophobic effect associated with electrospray ionization resulted in a higher abundance of the hydrophobic molecule. This bias was eliminated when the air amplifier was turned ON and a response indicative of the respective component concentrations of the molecules in the bulk solution was observed. PMID:17855111

  14. Slow step of oxygen ionization at oxide electrocatalysts

    SciTech Connect

    Trunov, A.M.

    1987-02-01

    The authors construct a mathematical model which depicts the electrochemical behavior of an oxide powder electrocatalyst and the chemisorption and ionization of the oxygen molecule on the electrode. The model is used to construct both the anodic and cathodic polarization curves as well as assess the electrochemical reaction rate and the electron behavior.

  15. 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.

  16. High-level ab initio predictions for the ionization energies and heats of formation of five-membered-ring molecules: thiophene, furan, pyrrole, 1,3-cyclopentadiene, and borole, C4H4X/C4H4X+ (X = S, O, NH, CH2, and BH).

    PubMed

    Lo, Po-Kam; Lau, Kai-Chung

    2011-02-10

    The ionization energies (IEs) and heats of formation (ΔH°(f0)/ΔH°(f298)) for thiophene (C(4)H(4)S), furan (C(4)H(4)O), pyrrole (C(4)H(4)NH), 1,3-cyclopentadiene (C(4)H(4)CH(2)), and borole (C(4)H(4)BH) have been calculated by the wave function-based ab initio CCSD(T)/CBS approach, which involves the approximation to the complete basis set (CBS) limit at the coupled-cluster level with single and double excitations plus a quasi-perturbative triple excitation [CCSD(T)]. Where appropriate, the zero-point vibrational energy correction (ZPVE), the core-valence electronic correction (CV), and the scalar relativistic effect (SR) are included in these calculations. The respective CCSD(T)/CBS predictions for C(4)H(4)S, C(4)H(4)O, C(4)H(4)NH, and C(4)H(4)CH(2), being 8.888, 8.897, 8.222, and 8.582 eV, are in excellent agreement with the experimental values obtained from previous photoelectron and photoion measurements. The ΔH°(f0)/ΔH°(f298) values for the aforementioned molecules and their corresponding cations have also been predicted by the CCSD(T)/CBS method, and the results are compared with the available experimental data. The comparisons between the CCSD(T)/CBS predictions and the experimental values for C(4)H(4)S, C(4)H(4)O, C(4)H(4)NH, and C(4)H(4)CH(2) suggest that the CCSD(T)/CBS procedure is capable of predicting reliable IE values for five-membered-ring molecules with an uncertainty of ±13 meV. In view of the excellent agreements between the CCSD(T)/CBS predictions and the experimental values for C(4)H(4)S, C(4)H(4)O, C(4)H(4)NH, and C(4)H(4)CH(2), the similar CCSD(T)/CBS IE and ΔH°(f0)/ΔH°(f298) predictions for C(4)H(4)BH, whose thermochemical data are not readily available due to its reactive nature, should constitute a reliable data set. The CCSD(T)/CBS IE(C(4)H(4)BH) value is 8.868 eV, and ΔH°(f0)/ΔH°(f298) values for C(4)H(4)BH and C(4)H(4)BH(+) are 269.5/258.6 and 1125.1/1114.6 kJ/mol, respectively. The highest occupied molecular orbitals

  17. 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.

  18. Electron impact ionization of cycloalkanes, aldehydes, and ketones

    SciTech Connect

    Gupta, Dhanoj; Antony, Bobby

    2014-08-07

    The theoretical calculations of electron impact total ionization cross section for cycloalkane, aldehyde, and ketone group molecules are undertaken from ionization threshold to 2 keV. The present calculations are based on the spherical complex optical potential formalism and complex scattering potential ionization contribution method. The results of most of the targets studied compare fairly well with the recent measurements, wherever available and the cross sections for many targets are predicted for the first time. The correlation between the peak of ionization cross sections with number of target electrons and target parameters is also reported. It was found that the cross sections at their maximum depend linearly with the number of target electrons and with other target parameters, confirming the consistency of the values reported here.

  19. 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.

  20. 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.

  1. 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

  2. Ultrahigh vacuum measuring ionization gauge

    NASA Technical Reports Server (NTRS)

    Brock, F. J. (Inventor)

    1968-01-01

    The ionization gage described consists of separate ionization and collector regions connected at an exit area with a modulator electrode. In addition to the standard modulation function, the modulator in this location yields a suprising increase in collector current, apparently due to improved focussing and extraction of ions from the ionization region.

  3. Resonance ionization of sputtered atoms: Quantitative analysis in the near-surface region of silicon wafers

    NASA Astrophysics Data System (ADS)

    Calaway, W. F.; Spiegel, D. R.; Marshall, A. H.; Downey, S. W.; Pellin, M. J.

    1997-02-01

    The unambiguous identification and quantification of low levels of metallic impurities on Si wafers are difficult problems due to the rapidly changing chemical activity near the surface. Air-exposed Si surfaces typically possess a native oxide layer several atoms thick plus a top monolayer of various silicon-containing molecules. Resonance ionization spectroscopy (RIS) used for postionization in secondary neutral mass spectrometry (SNMS) is uniquely suited to this task. The high sensitivity of this technique allows detection of metals at parts per billion levels with monolayer sensitivity. The high selectivity of RIS allows unambiguous identification of elements, while the reduced matrix effects of SNMS allow quantification of the photoionized element. Characterization of Si surfaces using RIS/SNMS has been explored by measuring the concentration profiles of Ca in the near-surface region of Si wafers of varying degrees of cleanliness. Calcium detection can be problematic due to the isobaric interference with SiC, particularly in the near-surface region during fabrication of devices due to the use of organic photoresist. Three different resonance ionization schemes for Ca have been examined and compared for effectiveness by calculating detection limits for Ca in Si in the chemically active near-surface region.

  4. Attosecond-Recollision-Controlled Selective Fragmentation of Polyatomic Molecules

    NASA Astrophysics Data System (ADS)

    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

    2012-12-01

    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.

  5. 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. PMID:23368312

  6. 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 ...

  7. 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

  8. 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.

  9. 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.

  10. 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

  11. MALDI- or ESI? Pros and cons for protein and small molecules

    SciTech Connect

    Olivares, J. A.

    2004-01-01

    Mass spectrometry has become a very popular technique in the analytical characterization of elements and molecules that range from inorganic, organic, and biological species. This popularity has soared in the past 15 years primarily through the development of ionization sources that can easily ionize large organic and biological molecules, intact and/or with controlled fragmentation. The two primary ionization mechanisms responsible for this capability are Matrix Assisted Laser Desorption Ionization (MALDI) and Electrospray Ionization (ESI). The development of the latter resulted in the 2002 Nobel Prize in Chemistry Engineering for John Fenn. This capability has presented a new paradigm allowing the field of proteomics to break through, with the characterization of major fractions of the proteins in a biological cell. The sensitivity, specificity, and structural characterization of available today using these techniques will be discussed with some examples in the characterization of both large and small molecules and relative merits of each technology.

  12. Field-ionization threshold and its induced ionization-window phenomenon for Rydberg atoms in a short single-cycle pulse

    NASA Astrophysics Data System (ADS)

    Yang, B. C.; Robicheaux, F.

    2014-12-01

    We study the field-ionization threshold behavior when a Rydberg atom is ionized by a short single-cycle pulse field. Both hydrogen and sodium atoms are considered. The required threshold field amplitude is found to scale inversely with the binding energy when the pulse duration becomes shorter than the classical Rydberg period, and, thus, more weakly bound electrons require larger fields for ionization. This threshold scaling behavior is confirmed by both three-dimensional classical trajectory Monte Carlo simulations and numerically solving the time-dependent Schrödinger equation. More surprisingly, the same scaling behavior in the short pulse limit is also followed by the ionization thresholds for much lower bound states, including the hydrogen ground state. An empirical formula is obtained from a simple model, and the dominant ionization mechanism is identified as a nonzero spatial displacement of the electron. This displacement ionization should be another important mechanism beyond the tunneling ionization and the multiphoton ionization. In addition, an "ionization window" is shown to exist for the ionization of Rydberg states, which may have potential applications to selectively modify and control the Rydberg-state population of atoms and molecules.

  13. 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.

  14. 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.

  15. Atmospheric-pressure Penning ionization mass spectrometry.

    PubMed

    Hiraoka, Kenzo; Fujimaki, Susumu; Kambara, Shizuka; Furuya, Hiroko; Okazaki, Shigemitsu

    2004-01-01

    A preliminary study on the atmospheric-pressure Penning ionization (APP(e)I) of gaseous organic compounds with Ar* has been made. The metastable argon atoms (Ar*: 11.55 eV for (3)P(2) and 11.72 eV for (3)P(0)) were generated by the negative-mode corona discharge of atmospheric-pressure argon gas. By applying a high positive voltage (+500 to +1000 V) to the stainless steel capillary for the sample introduction (0.1 mm i.d., 0.3 mm o.d.), strong ion signals could be obtained. The ions formed were sampled through an orifice into the vacuum and mass-analyzed by an orthogonal time-of-flight mass spectrometer. The major ions formed by APP(e)I are found to be molecular-related ions for alkanes, aromatics, and oxygen-containing compounds. Because only the molecules with ionization energies less than the internal energy of Ar* are ionized, the present method will be a selective and highly sensitive interface for gas chromatography/mass spectrometry. PMID:15384154

  16. 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.

  17. Comparison Study of Atomic and Molecular Single Ionization in the Multiphoton Ionization Regime

    SciTech Connect

    Wu Jian; Zeng Heping; Guo Chunlei

    2006-06-23

    In this Letter, we report, for the first time in the multiphoton ionization regime, a comparison study of single-electron ionization of diatomic molecules versus rare gas atoms with virtually the same ionization potentials. In comparing N{sub 2}{sup +} to Ar{sup +}, a higher ion signal is seen in N{sub 2}{sup +} compared to Ar{sup +} for linear polarization but the difference vanishes in circularly polarized light. In comparing O{sub 2}{sup +} to Xe{sup +}, we observe a suppression in O{sub 2}{sup +} compared to Xe{sup +} for both linear and circular polarization but this suppression exhibits an intensity dependence; i.e., there is little suppression for O{sub 2}{sup +} at the lowest intensity range, but the suppression becomes increasingly stronger as the laser intensity increases. The multielectron screening model is used to discuss possible mechanisms of this intensity dependent suppression in O{sub 2}{sup +} in the multiphoton ionization regime.

  18. 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

  19. Rovibrationally selected ion-molecule collision study using the molecular beam vacuum ultraviolet laser pulsed field ionization-photoion method: Charge transfer reaction of N{sub 2}{sup +}(X {sup 2}{Sigma}{sub g}{sup +}; v{sup +}= 0-2; N{sup +}= 0-9) + Ar

    SciTech Connect

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

    2012-09-14

    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 N{sub 2}{sup +}(v{sup +}, N{sup +}) + 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 N{sub 2}{sup +}(X {sup 2}{Sigma}{sub g}{sup +}, v{sup +}= 0-2, N{sup +}= 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 N{sub 2}{sup +} PFI-PI beam can be formed with a laboratory kinetic energy resolution of {Delta}E{sub lab}={+-} 50 meV. As a result, the total cross section measurement can be conducted at center-of-mass kinetic energies (E{sub cm}'s) down to thermal energies. Absolute total rovibrationally selected cross sections {sigma}(v{sup +}= 0-2, N{sup +}= 0-9) for the N{sub 2}{sup +}(X {sup 2}{Sigma}{sub g}{sup +}; v{sup +}= 0-2, N{sup +}= 0-9) + Ar CT reaction have been measured in the E{sub cm} range of 0.04-10.0 eV, revealing strong vibrational enhancements and E{sub cm}-dependencies of {sigma}(v{sup +}= 0-2, N{sup +}= 0-9). The thermochemical threshold at E{sub cm}= 0.179 eV for the formation of Ar{sup +} from N{sub 2}{sup +}(X; v{sup +}= 0, N{sup +}) + Ar was observed by the measured {sigma}(v{sup +}= 0), confirming the narrow {Delta}E{sub cm} spread achieved in

  20. 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.

  1. 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.

  2. Single-Molecule Solvation-Shell Sensing

    NASA Astrophysics Data System (ADS)

    Leary, E.; Höbenreich, H.; Higgins, S. J.; van Zalinge, H.; Haiss, W.; Nichols, R. J.; Finch, C. M.; Grace, I.; Lambert, C. J.; McGrath, R.; Smerdon, J.

    2009-02-01

    We present a new route to single-molecule sensing via solvation shells surrounding a current-carrying backbone molecule. As an example, we show that the presence of a water solvation shell “gates” the conductance of a family of oligothiophene-containing molecular wires, and that the longer the oligothiophene, the larger is the effect. For the longest example studied, the molecular conductance is over 2 orders of magnitude larger in the presence of a shell comprising just 10 water molecules. A first principles theoretical investigation of electron transport through the molecules, using the nonequilibrium Green’s function method, shows that water molecules interact directly with the thiophene rings, significantly shifting transport resonances and greatly increasing the conductance. This reversible effect is confirmed experimentally through conductance measurements performed in the presence of moist air and dry argon.

  3. Nuclear-Electronic Coherence in Strong-Field Dissociative Ionization

    NASA Astrophysics Data System (ADS)

    Yu, Youliang; Wang, Yujun; Zeng, Shuo; Esry, B. D.

    2015-05-01

    In strong-field dissociative ionization of molecules, the ionization step is usually modeled since direct calculation is very challenging. In most of the models used to date, ionization is assumed to occur at several well-defined times accompanied by promotion of a nuclear wave packet to the ionic Born-Oppenheimer potential. Whether these nuclear wave packets should add coherently or incoherently in general is an open question. To answer it, we solve the time-dependent Schrödinger equation for one-dimensional H2+,where ionization is included naturally, and compare the observables, such as the kinetic energy release spectrum, with those from an ionization model. We then examine the validity of such models in strong-field dissociative ionization of H2+with reduced dimensionality. We do not, however, expect this physics to depend sensitively on the dimensionality. Supported by the Chemical Sciences, Geosciences, and Biosciences Division, Office of Basic Energy Sciences, Office of Science, U.S. Department of Energy.

  4. Rationally designed donor-acceptor scheme based molecules for applications in opto-electronic devices.

    PubMed

    Subash Sundar, T; Sen, R; Johari, P

    2016-04-01

    Several donor (D)-acceptor (A) based molecules are rationally designed by adopting three different schemes in which the conjugation length, strength of the donor and acceptor moieties, and planarity of the molecules are varied. These variations are made by introducing a π-conjugated linkage unit, terminating the ends of the moieties by different electron donating and accepting functional groups, and fusing the donor and acceptor moieties, respectively. Our DFT and TDDFT based calculations reveal that using the above-mentioned design schemes, the electronic and optical properties of the D-A based molecules can be largely tuned. While introduction of a linkage and fusing of moieties enhance the π-π interaction, addition of electron donating groups (-CH3, -OH, and -NH2) and electron accepting groups (-CF3, -CN, -NO2, and -NH3(+)) varies the strength of the donor and acceptor moieties. These factors lead to modulation of the HOMO and LUMO energy levels and facilitate the engineering of the HOMO-LUMO gap and the optical gap over a wide range of ∼0.7-3.7 eV. Moreover, on the basis of calculated ionization potential and reorganization energy, most of the investigated molecules are predicted to be air stable and to exhibit high electron mobility, with the possibility of the presence of ambipolar characteristics in a few of them. The results of our calculations not only demonstrate the examined molecules to be the potential materials for organic opto-electronic devices, but also establish an understanding of the composition-structure-property correlation, which will provide guidelines for designing and synthesizing new materials of choice. PMID:26972386

  5. 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.

  6. 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.

  7. Femtosecond spectroscopy of molecules and clusters

    SciTech Connect

    Baumert, T.; Gerber, G.

    1995-12-31

    In the molecular physics section of this report we first discuss the evolution of a vibrational wavepacket in a double minimum potential well. Second, we will focus on the dynamics of multiphoton ionization (MPI) in a diatomic, and we will see how the unexpected results give new input into the challenging field of controlling chemical reactions by means of time-resolved laser techniques. As high laser intensities are achieved in focused ultrashort light pulses, their interaction with molecules is of particular interest and will be treated next. For all these experiments we have chosen the Na{sub 2} molecule as a model system, as there is a wealth of spectroscopic and theoretical information available, which facilitates the interpretation of the time domain results considerably. In the cluster section of this chapter we report the first experiments in cluster physics employing ultrashort laser pulses to time-resolved studies of cluster ionization and fragmentation processes. Clusters and in particular metal clusters have been the fascinating subject of many experimental and theoretical studies. Clusters form the link between solid-state physics and molecular physics. Metal clusters exhibit distinct features ranging from molecular properties seen in small particles to the solid state like behavior of larger aggregates. Studies of cluster properties like geometric structures, the evolution of the electronic states from localized to delocalized in nature, and the real-time dynamics of ionization and fragmentation have not yet been performed in detail as a function of cluster size.

  8. 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.

  9. 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

  10. Air Pollution

    MedlinePlus

    Air pollution is a mixture of solid particles and gases in the air. Car emissions, chemicals from factories, dust, ... a gas, is a major part of air pollution in cities. When ozone forms air pollution, it's ...

  11. 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 ...

  12. 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.

  13. Plasma Production via Field Ionization

    SciTech Connect

    O'Connell, C.L.; Barnes, C.D.; Decker, F.; Hogan, M.J.; Iverson, R.; Krejcik, P.; Siemann, R.; Walz, D.R.; Clayton, C.E.; Huang, C.; Johnson, D.K.; Joshi, C.; Lu, W.; Marsh, K.A.; Mori, W.; Zhou, M.; Deng, S.; Katsouleas, T.; Muggli, P.; Oz, E.; /Southern California U.

    2007-01-02

    Plasma production via field ionization occurs when an incoming particle beam is sufficiently dense that the electric field associated with the beam ionizes a neutral vapor or gas. Experiments conducted at the Stanford Linear Accelerator Center explore the threshold conditions necessary to induce field ionization by an electron beam in a neutral lithium vapor. By independently varying the transverse beam size, number of electrons per bunch or bunch length, the radial component of the electric field is controlled to be above or below the threshold for field ionization. Additional experiments ionized neutral xenon and neutral nitric oxide by varying the incoming beam's bunch length. A self-ionized plasma is an essential step for the viability of plasma-based accelerators for future high-energy experiments.

  14. 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)

  15. Characterization of Nonpolar Lipids and Selected Steroids by Using Laser-Induced Acoustic Desorption/Chemical Ionization, Atmospheric Pressure Chemical Ionization, and Electrospray Ionization Mass Spectrometry†

    PubMed Central

    Jin, Zhicheng; Daiya, Shivani; Kenttämaa, Hilkka I.

    2011-01-01

    Laser-induced acoustic desorption (LIAD) combined with ClMn(H2O)+ chemical ionization (CI) was tested for the analysis of nonpolar lipids and selected steroids in a Fourier-transform ion cyclotron resonance mass spectrometer (FT-ICR). The nonpolar lipids studied, cholesterol, 5α-cholestane, cholesta-3,5-diene, squalene, and β-carotene, were found to solely form the desired water replacement product (adduct-H2O) with the ClMn(H2O)+ ions. The steroids, androsterone, dehydroepiandrosterone (DHEA), estrone, estradiol, and estriol, also form abundant adduct-H2O ions, but less abundant adduct-2H2O ions were also observed. Neither (+)APCI nor (+)ESI can ionize the saturated hydrocarbon lipid, cholestane. APCI successfully ionizes the unsaturated hydrocarbon lipids to form exclusively the intact protonated analytes. However, it causes extensive fragmentation for cholesterol and the steroids. The worst case is cholesterol that does not produce any stable protonated molecules. On the other hand, ESI cannot ionize any of the hydrocarbon analytes, saturated or unsaturated. However, ESI can be used to protonate the oxygen-containing analytes with substantially less fragmentation than for APCI in all cases except for cholesterol and estrone. In conclusion, LIAD/ClMn(H2O)+ chemical ionization is superior over APCI and ESI for the mass spectrometric characterization of underivatized nonpolar lipids and steroids. PMID:21528012

  16. 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)

  17. 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

  18. Atmospheric pressure chemical ionization of explosives using alternating current corona discharge ion source.

    PubMed

    Usmanov, D T; Chen, L C; Yu, Z; Yamabe, S; Sakaki, S; Hiraoka, K

    2015-04-01

    The high-sensitive detection of explosives is of great importance for social security and safety. In this work, the ion source for atmospheric pressure chemical ionization/mass spectrometry using alternating current corona discharge was newly designed for the analysis of explosives. An electromolded fine capillary with 115 µm inner diameter and 12 mm long was used for the inlet of the mass spectrometer. The flow rate of air through this capillary was 41 ml/min. Stable corona discharge could be maintained with the position of the discharge needle tip as close as 1 mm to the inlet capillary without causing the arc discharge. Explosives dissolved in 0.5 µl methanol were injected to the ion source. The limits of detection for five explosives with 50 pg or lower were achieved. In the ion/molecule reactions of trinitrotoluene (TNT), the discharge products of NOx (-) (x = 2,3), O3 and HNO3 originating from plasma-excited air were suggested to contribute to the formation of [TNT - H](-) (m/z 226), [TNT - NO](-) (m/z 197) and [TNT - NO + HNO3 ](-) (m/z 260), respectively. Formation processes of these ions were traced by density functional theory calculations. Copyright © 2015 John Wiley & Sons, Ltd. PMID:26149109

  19. 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.

  20. 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.

  1. 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. PMID:26824537

  2. Low pressure microplasmas enabled by field ionization: Kinetic modeling

    NASA Astrophysics Data System (ADS)

    Macheret, Sergey O.; Tholeti, Siva Sashank; Alexeenko, Alina A.

    2016-05-01

    A principle of microplasma generation that utilizes field emission of electrons at the cathode and field ionization producing ions at the anode, both processes relying on nanorods or nanotubes, is explored theoretically. In this plasma generation concept, collisional ionization of atoms and molecules by electron impact would play a negligible role. Analytical estimates as well as plasma kinetic modeling by particle-in-cell method with Monte Carlo collisions in argon confirm that this principle can enable substantial plasma densities at near-collisionless microgaps, while requiring relatively low voltages, less than 100 V. An order of magnitude increase in electron number density can be achieved due to enhancement of field emission at the cathode by positive space charge at high field ionization ion current densities.

  3. 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.

  4. 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.

  5. 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.

  6. 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.

  7. 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.

  8. 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.

  9. 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.

  10. 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.

  11. FAST TRACK COMMUNICATION: Attosecond correlation dynamics during electron tunnelling from molecules

    NASA Astrophysics Data System (ADS)

    Walters, Zachary B.; Smirnova, Olga

    2010-08-01

    In this communication, we present an analytical theory of strong-field ionization of molecules, which takes into account the rearrangement of multiple interacting electrons during the ionization process. We show that such rearrangement offers an alternative pathway to the ionization of orbitals more deeply bound than the highest occupied molecular orbital. This pathway is not subject to the full exponential suppression characteristic of direct tunnel ionization from the deeper orbitals. The departing electron produces an 'attosecond correlation pulse' which controls the rearrangement during the tunnelling process. The shape and duration of this pulse are determined by the electronic structure of the relevant states, molecular orientation and laser parameters.

  12. 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

  13. 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.

  14. Extracting Structure Parameters of Dimers for Molecular Tunneling Ionization Model

    NASA Astrophysics Data System (ADS)

    Song-Feng, Zhao; Fang, Huang; Guo-Li, Wang; Xiao-Xin, Zhou

    2016-03-01

    We determine structure parameters of the highest occupied molecular orbital (HOMO) of 27 dimers for the molecular tunneling ionization (so called MO-ADK) model of Tong et al. [Phys. Rev. A 66 (2002) 033402]. The molecular wave functions with correct asymptotic behavior are obtained by solving the time-independent Schrödinger equation with B-spline functions and molecular potentials which are numerically created using the density functional theory. We examine the alignment-dependent tunneling ionization probabilities from MO-ADK model for several molecules by comparing with the molecular strong-field approximation (MO-SFA) calculations. We show the molecular Perelomov–Popov–Terent'ev (MO-PPT) can successfully give the laser wavelength dependence of ionization rates (or probabilities). Based on the MO-PPT model, two diatomic molecules having valence orbital with antibonding systems (i.e., Cl2, Ne2) show strong ionization suppression when compared with their corresponding closest companion atoms. Supported by National Natural Science Foundation of China under Grant Nos. 11164025, 11264036, 11465016, 11364038, the Specialized Research Fund for the Doctoral Program of Higher Education of China under Grant No. 20116203120001, and the Basic Scientific Research Foundation for Institution of Higher Learning of Gansu Province

  15. Extracting Structure Parameters of Dimers for Molecular Tunneling Ionization Model

    NASA Astrophysics Data System (ADS)

    Zhao, Song-Feng; Huang, Fang; Wang, Guo-Li; Zhou, Xiao-Xin

    2016-03-01

    We determine structure parameters of the highest occupied molecular orbital (HOMO) of 27 dimers for the molecular tunneling ionization (so called MO-ADK) model of Tong et al. [Phys. Rev. A 66 (2002) 033402]. The molecular wave functions with correct asymptotic behavior are obtained by solving the time-independent Schrödinger equation with B-spline functions and molecular potentials which are numerically created using the density functional theory. We examine the alignment-dependent tunneling ionization probabilities from MO-ADK model for several molecules by comparing with the molecular strong-field approximation (MO-SFA) calculations. We show the molecular Perelomov-Popov-Terent'ev (MO-PPT) can successfully give the laser wavelength dependence of ionization rates (or probabilities). Based on the MO-PPT model, two diatomic molecules having valence orbital with antibonding systems (i.e., Cl2, Ne2) show strong ionization suppression when compared with their corresponding closest companion atoms. Supported by National Natural Science Foundation of China under Grant Nos. 11164025, 11264036, 11465016, 11364038, the Specialized Research Fund for the Doctoral Program of Higher Education of China under Grant No. 20116203120001, and the Basic Scientific Research Foundation for Institution of Higher Learning of Gansu Province

  16. 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.

  17. On the Several Molecules and Nanostructures of Water

    PubMed Central

    Whitney, Cynthia Kolb

    2012-01-01

    This paper investigates the water molecule from a variety of viewpoints. Water can involve different isotopes of Hydrogen and Oxygen, it can form differently shaped isomer molecules, and, when frozen, it occupies space differently than most other substances do. The tool for conducting the investigation of all this is called ‘Algebraic Chemistry’. This tool is a quantitative model for predicting the energy budget for all sorts of changes between different ionization states of atoms that are involved in chemical reactions and in changes of physical state. The model is based on consistent patterns seen in empirical data about ionization potentials, together with rational scaling laws that can interpolate and extrapolate for situations where no data are available. The results of the investigation of the water molecule include comments, both positive and negative, about technologies involving heavy water, poly water, Brown’s gas, and cold fusion. PMID:22312305

  18. On the several molecules and nanostructures of water.

    PubMed

    Whitney, Cynthia Kolb

    2012-01-01

    This paper investigates the water molecule from a variety of viewpoints. Water can involve different isotopes of Hydrogen and Oxygen, it can form differently shaped isomer molecules, and, when frozen, it occupies space differently than most other substances do. The tool for conducting the investigation of all this is called 'Algebraic Chemistry'. This tool is a quantitative model for predicting the energy budget for all sorts of changes between different ionization states of atoms that are involved in chemical reactions and in changes of physical state. The model is based on consistent patterns seen in empirical data about ionization potentials, together with rational scaling laws that can interpolate and extrapolate for situations where no data are available. The results of the investigation of the water molecule include comments, both positive and negative, about technologies involving heavy water, poly water, Brown's gas, and cold fusion. PMID:22312305

  19. IEHI: Ionization Equilibrium for Heavy Ions

    NASA Astrophysics Data System (ADS)

    Cranmer, Steven R.

    2015-07-01

    IEHI, written in Fortran, outputs a simple "coronal" ionization equilibrium (i.e., collisional ionization and auto-ionization balanced by radiative and dielectronic recombination) for a plasma at a given electron temperature.

  20. Biological effects of ionizing radiation at the molecular, cellular, and organismal levels. Triennial progress report, October 15, 1977-October 14, 1980

    SciTech Connect

    Lange, C.S.

    1980-01-01

    Two major accomplishments have been achieved in the past three years with the support of this contract. Firstly, the original Zimm theory of rotor speed dependent DNA sedimentation has been tested quantitatively and found to be correct, i.e., T4c and T4D+ DNAs sedimented with S/sup 0//sub 20,w/ values as predicted by the equation of Zimm and Schumaker. Furthermore, the quantitative validity of the theory means that the size (M/sub r/) of a DNA sedimenting under speed-dependent conditions is not undefinable but rather can be uniquely obtained by the application of that theory to the data. Secondly, the viscoelastic recoil (GAMMA/sub 11/), or more accurately, the zero shear rate reduced recoil (GAMMA/sub 11, r, o/) has been shown to be a quantitative direct function of the number of intact (T4c) DNA molecules present (per ml) in solution. This demonstration made possible the measurement of a direct survival curve for intact DNA molecules (i.e., without double-strand breaks) after exposure to ionizing radiation. A /sub DNA/D/sub 37/ of 47.4 krads was obtained for the DNA of T4c coliphage irradiated in air as a solution of phage particles. It is noteworthy that this survival curve measures the number of intact DNA molecules, not the average number of breaks/molecule.

  1. Initial Stage of the Microwave Ionization Wave Within a 1D Model

    NASA Astrophysics Data System (ADS)

    Semenov, V. E.; Rakova, E. I.; Glyavin, M. Yu.; Nusinovich, G. S.

    2016-06-01

    The dynamics of the microwave breakdown in a gas is simulated numerically within a simple 1D model which takes into account such processes as the impact ionization of gas molecules, the attachment of electrons to neutral molecules, and plasma diffusion. Calculations are carried out for different spatial distributions of seed electrons with account for reflection of the incident electromagnetic wave from the plasma. The results reveal considerable dependence of the ionization wave evolution on the relation between the field frequency and gas pressure, as well as on the existence of extended rarefied halo of seed electrons. At relatively low gas pressures (or high field frequencies), the breakdown process is accompanied by the stationary ionization wave moving towards the incident electromagnetic wave. In the case of a high gas pressure (or a relatively low field frequency), the peculiarities of the breakdown are associated with the formation of repetitive jumps of the ionization front.

  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. Development of an optical digital ionization chamber

    SciTech Connect

    Turner, J.E.; Hunter, S.R.; Hamm, R.N.; Wright, H.A.; Hurst, G.S.; Gibson, W.A.

    1988-01-01

    We are developing a new device for optically detecting and imaging the track of a charged particle in a gas. The electrons in the particle track are made to oscillate rapidly by the application of an external, short-duration, high-voltage, RF electric field. The excited electrons produce additional ionization and electronic excitation of the gas molecules in their immediate vicinity, leading to copious light emission (fluorescence) from the selected gas, allowing the location of the electrons along the track to be determined. Two digital cameras simultaneously scan the emitted light across two perpendicular planes outside the chamber containing gas. The information thus obtained for a given track can be used to infer relevant quantities for microdosimetry and dosimetry, e.g., energy deposited, LET, and track structure in the gas. The design of such a device now being constructed and methods of obtaining the dosimetric data from the digital output will be described. 4 refs., 4 figs.

  4. [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. PMID:22468530

  5. 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.

  6. Air Abrasion

    MedlinePlus

    ... delivered directly to your desktop! more... What Is Air Abrasion? Article Chapters What Is Air Abrasion? What Happens? The Pros and Cons Will I Feel Anything? Is Air Abrasion for Everyone? print full article print this ...

  7. 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.

  8. 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.

  9. 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.

  10. Imaging of alignment and structural changes of carbon disulfide molecules using ultrafast electron diffraction.

    PubMed

    Yang, Jie; Beck, Joshua; Uiterwaal, Cornelis J; Centurion, Martin

    2015-01-01

    Imaging the structure of molecules in transient-excited states remains a challenge due to the extreme requirements for spatial and temporal resolution. Ultrafast electron diffraction from aligned molecules provides atomic resolution and allows for the retrieval of structural information without the need to rely on theoretical models. Here we use ultrafast electron diffraction from aligned molecules and femtosecond laser mass spectrometry to investigate the dynamics in carbon disulfide following the interaction with an intense femtosecond laser pulse. We observe that the degree of alignment reaches an upper limit at laser intensities below the ionization threshold, and find evidence of structural deformation, dissociation and ionization at higher laser intensities. PMID:26337631

  11. Ultrafast laser time-of-flight mass analysis of laser-desorbed atoms and molecules

    NASA Astrophysics Data System (ADS)

    Hankin, S. M.; Robson, L.; Tasker, A. D.; Ledingham, K. W. D.; McCanny, T.; Singhal, R. P.; Kosmidis, C.; Tzallas, P.; Langley, A. J.; Taday, P. F.; Divall, E. J.

    2001-08-01

    Femtosecond time-of-fight mass spectra of laser-desorbed gallium arsenide (GaAs) and trinitrobenzene (TNT) reveal the characteristic features and differences of femtosecond atomic and molecular ionization. Significant yields of multiply-charged atomic fragments, parent molecular ions and structure-specific fragment ions of labile molecules have been obtained. An optimum desorption laser intensity for the transfer of neutral intact parent molecules in to the gas phase has been observed to be molecule-dependent. This work demonstrates the potential of ultrafast laser ionization and has significant implications for analytical and environmental studies of solid materials.

  12. 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.

  13. Recent advances in inorganic materials for LDI-MS analysis of small molecules.

    PubMed

    Shi, C Y; Deng, C H

    2016-05-10

    In this review, various inorganic materials were summarized for the analysis of small molecules by laser desorption/ionization mass spectrometry (LDI-MS). Due to its tremendous advantages, such as simplicity, high speed, high throughput, small analyte volumes and tolerance towards salts, LDI-MS has been widely used in various analytes. During the ionization process, a suitable agent is required to assist the ionization, such as an appropriate matrix for matrix assisted laser desorption/ionization mass spectrometry (MALDI-MS). However, it is normally difficult to analyze small molecules with the MALDI technique because conventional organic matrices may produce matrix-related peaks in the low molecular-weight region, which limits the detection of small molecules (m/z < 700 Da). Therefore, more and more inorganic materials, including carbon-based materials, silicon-based materials and metal-based materials, have been developed to assist the ionization of small molecules. These inorganic materials can transfer energy and improve the ionization efficiency of analytes. In addition, functionalized inorganic materials can act as both an adsorbent and an agent in the enrichment and ionization of small molecules. In this review, we mainly focus on present advances in inorganic materials for the LDI-MS analysis of small molecules in the last five years, which contains the synthetic protocols of novel inorganic materials and the detailed results achieved by inorganic materials. On the other hand, this review also summarizes the application of inorganic materials as adsorbents in the selective enrichment of small molecules, which provides a new field for the application of inorganic materials. PMID:27050451

  14. CHEMICAL PROCESSES IN PROTOPLANETARY DISKS. II. ON THE IMPORTANCE OF PHOTOCHEMISTRY AND X-RAY IONIZATION

    SciTech Connect

    Walsh, Catherine; Millar, T. J.; Nomura, Hideko; Aikawa, Yuri

    2012-03-10

    We investigate the impact of photochemistry and X-ray ionization on the molecular composition of, and ionization fraction in, a protoplanetary disk surrounding a typical T Tauri star. We use a sophisticated physical model, which includes a robust treatment of the radiative transfer of UV and X-ray radiation, and calculate the time-dependent chemical structure using a comprehensive chemical network. In previous work, we approximated the photochemistry and X-ray ionization; here, we recalculate the photoreaction rates using the explicit UV wavelength spectrum and wavelength-dependent reaction cross sections. We recalculate the X-ray ionization rate using our explicit elemental composition and X-ray energy spectrum. We find that photochemistry has a larger influence on the molecular composition than X-ray ionization. Observable molecules sensitive to the photorates include OH, HCO{sup +}, N{sub 2}H{sup +}, H{sub 2}O, CO{sub 2}, and CH{sub 3}OH. The only molecule significantly affected by the X-ray ionization is N{sub 2}H{sup +}, indicating that it is safe to adopt existing approximations of the X-ray ionization rate in typical T Tauri star-disk systems. The recalculation of the photorates increases the abundances of neutral molecules in the outer disk, highlighting the importance of taking into account the shape of the UV spectrum in protoplanetary disks. A recalculation of the photoreaction rates also affects the gas-phase chemistry due to the adjustment of the H/H{sub 2} and C{sup +}/C ratios. The disk ionization fraction is not significantly affected by the methods adopted to calculate the photochemistry and X-ray ionization. We determine that there is a probable 'dead zone' where accretion is suppressed, present in a layer, Z/R {approx}< 0.1-0.2, in the disk midplane, within R Almost-Equal-To 200 AU.

  15. 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.

  16. 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.

  17. 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.

  18. 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.

  19. 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.

  20. 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.