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Sample records for pressure-dependent electron attachment

  1. Dissociative Electron Attachment

    NASA Astrophysics Data System (ADS)

    Arreola, Esmeralda; Esmeralda Arreola Collaboration; Leigh Hargreaves Collaboration

    Since the pioneering work of Boudiaffa et al., it has been understood that electrons, even with energies near or below the ionization threshold, are capable of initiating strand-breaks in human DNA. This discovery raised important questions for cancer treatments, since sub-ionizing electrons are known to be the most copiously produced secondary product of radiation therapy. But even to date these factors are largely excluded from dosimetry calculations. This lack of inclusion is, at least in part, certainly due to the dearth of fundamental data describing low-energy electron interactions with nucleotide molecules that form the basis of DNA. Understanding of how such slow electrons are able to damage DNA remains incomplete, but the strongly peaked nature of Boudiaffa et al.'s data gives strong hints at resonantly driven collision processes. DNA damage is therefore most likely driven by ``dissociative electron attachment'' (DEA). DEA is a rather complicated process to model due to the coupling of electronic and nuclear degrees of freedom in the molecule. At the California State University Fullerton, we are currently commissioning a new spectrometer to study dissociation channels, reaction rates and orientation effects in DEA collisions between slow electrons and nucleotide molecules. At the meeting we will present design parameters and commissioning data for this new apparatus.

  2. Pressure dependence of Hexanitrostilbene Raman/ electronic absorption spectra to validate DFT EOS

    NASA Astrophysics Data System (ADS)

    Farrow, Darcie; Alam, Kathleen; Martin, Laura; Fan, Hongyou; Kay, Jeffrey; Wixom, Ryan

    2015-06-01

    Due to its thermal stability and low vapor pressure, Hexanitrostilbene (HNS) is often used in high-temperature or vacuum applications as a detonator explosive or in mild detonating fuse. Toward improving the accuracy of the equation of state used in hydrodynamic simulations of the performance of HNS, we have measured the Raman and electronic absorption spectra of this material under static pressure in a diamond anvil cell. Density functional theory calculations were used to simulate the pressure dependence of the Raman/Electronic spectra along the Hugoniot and 300K isotherm for comparison and to aid in interpreting the data. We will discuss changes in the electronic structure of HNS under pressure, validation of a DFT predicted equation of state (EOS), and using this data as a basis for understanding future pulsed Raman measurements on dynamically compressed HNS samples.

  3. Electron attachment to fluorocarbon radicals

    NASA Astrophysics Data System (ADS)

    Shuman, Nicholas

    2014-10-01

    Most plasma environments contain populations of short-lived species such as radicals, the chemistry of which can have significant effects on the overall chemistry of the system. However, few experimental measurements of the kinetics of electron attachment to radicals exist due to the inherent difficulties of working with transient species. Calculations from first principles have been attempted, but are arduous and, because electron attachment is so sensitive to the specifics of the potential surface, their accuracy has not been established. Electron attachment to small fluorocarbon radicals is particularly important, as the data are needed for predictive modeling of plasma etching of semiconductor materials, a key process in the industrial fabrication of microelectronics. We have recently developed a novel flowing afterglow technique to measure several types of otherwise difficult to study plasma processes, including thermal electron attachment to radicals. Variable Electron and Neutral Density Attachment Mass Spectrometry (VENDAMS) exploits dissociative electron attachment in a weakly ionized plasma as a radical source. Here, we apply VENDAMS to a series of halofluorocarbon precursors in order to measure the kinetics of thermal electron attachment to fluorocarbon radicals. Results are presented for CF2, CF3, C2F5,C2F3,1-C3F7, 2-C3F7, and C3F5 from 300 K to 900 K. Both the magnitude and the temperature dependences of rate coefficients as well as product branching between associative and dissociative attachment are highly system specific; however, thermal attachment to all species is inefficient, never exceeding 5% of the collision rate. The data are analyzed using a recently developed kinetic modeling approach, which uses extended Vogt-Wannier theory as a starting point, accounts for dynamic effects such as coupling between the electron and nuclear motions through empirically validated functional forms, and finally uses statistical theory to determine the fate of

  4. Pressure dependence of the structure and electronic properties of Sr3Ir2O7

    NASA Astrophysics Data System (ADS)

    Donnerer, C.; Feng, Z.; Vale, J. G.; Andreev, S. N.; Solovyev, I. V.; Hunter, E. C.; Hanfland, M.; Perry, R. S.; Rønnow, H. M.; McMahon, M. I.; Mazurenko, V. V.; McMorrow, D. F.

    2016-05-01

    We study the structural evolution of Sr3Ir2O7 as a function of pressure using x-ray diffraction. At a pressure of 54 GPa at room temperature, we observe a first-order structural phase transition, associated with a change from tetragonal to monoclinic symmetry and accompanied by a 4% volume collapse. Rietveld refinement of the high-pressure phase reveals a novel modification of the Ruddlesden-Popper structure, which adopts an altered stacking sequence of the perovskite bilayers. As the positions of the oxygen atoms could not be reliably refined from the data, we use density functional theory (local-density approximation+U +spin orbit) to optimize the crystal structure and to elucidate the electronic and magnetic properties of Sr3Ir2O7 at high pressure. In the low-pressure tetragonal phase, we find that the in-plane rotation of the IrO6 octahedra increases with pressure. The calculations further indicate that a bandwidth-driven insulator-metal transition occurs at ˜20 GPa, along with a quenching of the magnetic moment. In the high-pressure monoclinic phase, structural optimization resulted in complex tilting and rotation of the oxygen octahedra and strongly overlapping t2 g and eg bands. The t2 g bandwidth renders both the spin-orbit coupling and electronic correlations ineffectual in opening an electronic gap, resulting in a robust metallic state for the high-pressure phase of Sr3Ir2O7 .

  5. Pressure dependence of electronic properties of BaI{sub 2}

    SciTech Connect

    Kumar, Pradeep; Vedeshwar, Agnikumar G.

    2015-08-28

    We present Density Functional Theoretical (DFT) calculations of the electronic properties of scintillator material BaI{sub 2} under pressure which were carried out using Perdew-Burke-Ernzerhof genralized gradient approximation. We found that BaI{sub 2} is a direct band gap material with band gap calculated as 3.35 eV. The pressure effect on BaI{sub 2} indicates a linear monotonously decreasing band gap and increasing valence band width with pressure. We have observed the shifting of band extrema from the Γ point with pressure. The pressure coefficient of band gap is found to be −0.047 eV/GPa. The interatomic ionicity factor of BaI{sub 2} is found to be 0.51. Trends in bonding and ionicity under pressure are also discussed.

  6. Miniature Reversal Electron-Attachment Detector

    NASA Technical Reports Server (NTRS)

    Chutjian, Ara

    1994-01-01

    Miniature reversal electron-attachment detector (miniREAD) enables direct injection of air or vapor at atmospheric pressure from monitored area into mass-spectrometric instrument to detect explosives, narcotics, or other substances, vapors of which suspected of being present in low concentrations. In comparison with older reversal electron-attachment detector, miniREAD simpler in design; more rugged; and easier to build, repair, and maintain. In addition, probably more sensitive.

  7. Dynamics of dissociative electron attachment to ammonia

    NASA Astrophysics Data System (ADS)

    Rescigno, T. N.; Trevisan, C. S.; Orel, A. E.; Slaughter, D. S.; Adaniya, H.; Belkacem, A.; Weyland, Marvin; Dorn, Alexander; McCurdy, C. W.

    2016-05-01

    Ab initio theoretical studies and momentum-imaging experiments are combined to provide a consistent picture of the dynamics of dissociative electron attachment to ammonia through its 5.5- and 10.5-eV resonance channels. The present study clarifies the character and symmetry of the anion states involved and the dynamics that leads to the observed fragment-ion channels, their branching ratios, and angular distributions.

  8. Dissociative electron attachment studies on acetone

    SciTech Connect

    Prabhudesai, Vaibhav S. Tadsare, Vishvesh; Ghosh, Sanat; Gope, Krishnendu; Davis, Daly; Krishnakumar, E.

    2014-10-28

    Dissociative electron attachment (DEA) to acetone is studied in terms of the absolute cross section for various fragment channels in the electron energy range of 0–20 eV. H{sup −} is found to be the most dominant fragment followed by O{sup −} and OH{sup −} with only one resonance peak between 8 and 9 eV. The DEA dynamics is studied by measuring the angular distribution and kinetic energy distribution of fragment anions using Velocity Slice Imaging technique. The kinetic energy and angular distribution of H{sup −} and O{sup −} fragments suggest a many body break-up for the lone resonance observed. The ab initio calculations show that electron is captured in the multi-centered anti-bonding molecular orbital which would lead to a many body break-up of the resonance.

  9. High resolution electron attachment to CO₂ clusters.

    PubMed

    Denifl, Stephan; Vizcaino, Violaine; Märk, Tilmann D; Illenberger, Eugen; Scheier, Paul

    2010-01-01

    Electron attachment to CO₂ clusters performed at high energy resolution (0.1 eV) is studied for the first time in the extended electron energy range from threshold (0 eV) to about 10 eV. Dissociative electron attachment (DEA) to single molecules yields O(-) as the only fragment ion arising from the well known (2)Π(u) shape resonance (ion yield centered at 4.4 eV) and a core excited resonance (at 8.2 eV). On proceeding to CO₂ clusters, non-dissociated complexes of the form (CO₂)(n)(-) including the monomer CO₂(-) are generated as well as solvated fragment ions of the form (CO₂)(n)O(-). The non-decomposed complexes appear already within a resonant feature near threshold (0 eV) and also within a broad contribution between 1 and 4 eV which is composed of two resonances observed for example for (CO₂)(4)(-) at 2.2 eV and 3.1 eV (peak maxima). While the complexes observed around 3.1 eV are generated via the (2)Π(u) resonance as precursor with subsequent intracluster relaxation, the contribution around 2.2 eV can be associated with a resonant scattering feature, recently discovered in single CO₂ in the selective excitation of the higher energy member of the well known Fermi dyad [M. Allan, Phys. Rev. Lett., 2001, 87, 0332012]. Formation of (CO₂)(n)(-) in the threshold region involves vibrational Feshbach resonances (VFRs) as previously discovered via an ultrahigh resolution (1 meV) laser photoelectron attachment method [E. Leber, S. Barsotti, I. I. Fabrikant, J. M. Weber, M.-W. Ruf and H. Hotop, Eur. Phys. J. D, 2000, 12, 125]. The complexes (CO₂)(n)O(-) clearly arise from DEA at an individual molecule within the cluster involving both the (2)Π(u) and the core excited resonance. PMID:21491691

  10. Pressure dependence of the configurational bistability and deep electronic levels of the MFe center in InP

    NASA Astrophysics Data System (ADS)

    Samara, G. A.; Barnes, C. E.

    2006-04-01

    The influence of hydrostatic pressure on the structural bistability and electronic properties of the processing-induced MFe center in Fe-doped n -type InP was investigated. Earlier work has shown that, when occupied by electrons, the center can be reversibly placed in either of two configurations, termed A and B , by the proper choice of electric biasing conditions and temperature. Pressure strongly modifies the energetics and kinetics of the various electronic transitions and of the transformations associated with the center. The activation volumes (ΔV*) for these processes were determined. In the absence of barriers to electron capture, or for small barriers, ΔV* can be interpreted as the breathing mode relaxation associated with electron emission or capture. At pressures ⩾8kbar , the center exists only in the A configuration regardless of bias conditions, because at these pressures the energetics and kinetics of the various processes have changed so much as to always favor the A configuration. It is also shown that, whereas the A⇄B transformations are charge state controlled at 1bar , this is not the case at high pressure where the transformations can be brought about without electron emission or hole capture. Earlier tentative atomic models for the center are discussed, and it is shown that some features of one of the models including the signs of the breathing mode relaxations associated with the various electron emissions are consistent with the experimental results, but issues remain. The results are also found to be generally consistent with first-principles calculations on defects in InP, but it is emphasized that whereas these calculations are for simple defects, the defects associated with the MFe center are more complex.

  11. Pressure dependence of electronic structure and superconductivity of the MnX (X = N, P, As, Sb).

    PubMed

    Chong, XiaoYu; Jiang, YeHua; Zhou, Rong; Feng, Jing

    2016-01-01

    A recently experimental discovered (Cheng et al., Phys. Rev. Lett. 114, 117001 (2015)) of superconductivity on the border of long-range magnetic order in the itinerant-electron helimagnet MnP via the application of high pressure makes MnP the first Mn-based superconductor. In this paper, we carry out first-principles calculations on MnX (X = N, P, As, Sb) and find superconducting critical temperature TC of MnP sharply increases near the critical pressure PC ≈ 8 GPa, which is in good agreement with the experiments. Electron-phonon coupling constant λ and electronic density of states at the Fermi level N (EF) are found to increase with pressure for MnP, which lead to the increase of TC of MnP. Moreover, we also find that the TC of MnAs and MnSb are higher than MnP, implying that the MnAs and MnSb may be the more potential Mn-based superconducting materials. PMID:26902857

  12. Pressure dependence of electronic structure and superconductivity of the MnX (X = N, P, As, Sb)

    PubMed Central

    Chong, XiaoYu; Jiang, YeHua; Zhou, Rong; Feng, Jing

    2016-01-01

    A recently experimental discovered (Cheng et al., Phys. Rev. Lett. 114, 117001 (2015)) of superconductivity on the border of long-range magnetic order in the itinerant-electron helimagnet MnP via the application of high pressure makes MnP the first Mn-based superconductor. In this paper, we carry out first-principles calculations on MnX (X = N, P, As, Sb) and find superconducting critical temperature TC of MnP sharply increases near the critical pressure PC ≈ 8 GPa, which is in good agreement with the experiments. Electron-phonon coupling constant λ and electronic density of states at the Fermi level N (EF) are found to increase with pressure for MnP, which lead to the increase of TC of MnP. Moreover, we also find that the TC of MnAs and MnSb are higher than MnP, implying that the MnAs and MnSb may be the more potential Mn-based superconducting materials. PMID:26902857

  13. Pressure dependence of electronic structure and superconductivity of the MnX (X = N, P, As, Sb)

    NASA Astrophysics Data System (ADS)

    Chong, Xiaoyu; Jiang, Yehua; Zhou, Rong; Feng, Jing

    2016-02-01

    A recently experimental discovered (Cheng et al., Phys. Rev. Lett. 114, 117001 (2015)) of superconductivity on the border of long-range magnetic order in the itinerant-electron helimagnet MnP via the application of high pressure makes MnP the first Mn-based superconductor. In this paper, we carry out first-principles calculations on MnX (X = N, P, As, Sb) and find superconducting critical temperature TC of MnP sharply increases near the critical pressure PC ≈ 8 GPa, which is in good agreement with the experiments. Electron-phonon coupling constant λ and electronic density of states at the Fermi level N (EF) are found to increase with pressure for MnP, which lead to the increase of TC of MnP. Moreover, we also find that the TC of MnAs and MnSb are higher than MnP, implying that the MnAs and MnSb may be the more potential Mn-based superconducting materials.

  14. Dynamics of Dissociative Electron Attachment to Methane

    NASA Astrophysics Data System (ADS)

    Rescigno, T. N.; Douguet, N.; Fonseca, S.; Orel, A. E.; Slaughter, D. S.; Belkacem, A.

    2015-05-01

    We present the results of a theoretical ad experimental study of dissociative electron attachment (DEA) to CH4. The total DEA cross section is dominated by a single broad peak centered near 10 eV, leading predominantly to H-/CH4 and CH2-/CH4dissociation channels. We will present evidence that both of these ion channels result from excitation of a triply degenerate Feshbach resonance (doubly excited negative ion state) of 2T2 symmetry whose parent is the lowest excited triplet state of the neutral molecule. We will present calculated angular distributions based on analysis of the entrance amplitudes obtained from the results of complex Kohn scattering calculations along with experimentally measured angular distributions obtained using the COLTRIMS method. Work performed under the auspices of the US DOE by the LBNL and supported by the U.S. DOE Office of Basic Energy Sciences, Division of Chemical Sciences.

  15. Date Attachable Offline Electronic Cash Scheme

    PubMed Central

    Sun, Wei-Zhe; Hau, Hoi-Tung

    2014-01-01

    Electronic cash (e-cash) is definitely one of the most popular research topics in the e-commerce field. It is very important that e-cash be able to hold the anonymity and accuracy in order to preserve the privacy and rights of customers. There are two types of e-cash in general, which are online e-cash and offline e-cash. Both systems have their own pros and cons and they can be used to construct various applications. In this paper, we pioneer to propose a provably secure and efficient offline e-cash scheme with date attachability based on the blind signature technique, where expiration date and deposit date can be embedded in an e-cash simultaneously. With the help of expiration date, the bank can manage the huge database much more easily against unlimited growth, and the deposit date cannot be forged so that users are able to calculate the amount of interests they can receive in the future correctly. Furthermore, we offer security analysis and formal proofs for all essential properties of offline e-cash, which are anonymity control, unforgeability, conditional-traceability, and no-swindling. PMID:24982931

  16. Date attachable offline electronic cash scheme.

    PubMed

    Fan, Chun-I; Sun, Wei-Zhe; Hau, Hoi-Tung

    2014-01-01

    Electronic cash (e-cash) is definitely one of the most popular research topics in the e-commerce field. It is very important that e-cash be able to hold the anonymity and accuracy in order to preserve the privacy and rights of customers. There are two types of e-cash in general, which are online e-cash and offline e-cash. Both systems have their own pros and cons and they can be used to construct various applications. In this paper, we pioneer to propose a provably secure and efficient offline e-cash scheme with date attachability based on the blind signature technique, where expiration date and deposit date can be embedded in an e-cash simultaneously. With the help of expiration date, the bank can manage the huge database much more easily against unlimited growth, and the deposit date cannot be forged so that users are able to calculate the amount of interests they can receive in the future correctly. Furthermore, we offer security analysis and formal proofs for all essential properties of offline e-cash, which are anonymity control, unforgeability, conditional-traceability, and no-swindling. PMID:24982931

  17. Imaging the molecular dynamics of dissociative electron attachment to water

    SciTech Connect

    Adaniya, Hidihito; Rudek, B.; Osipov, Timur; Haxton, Dan; Weber, Thorsten; Rescigno, Thomas N.; McCurdy, C.W.; Belkacem, Ali

    2009-10-19

    Momentum imaging experiments on dissociative electron attachment to the water molecule are combined with ab initio theoretical calculations of the angular dependence of the quantum mechanical amplitude for electron attachment to provide a detailed picture of the molecular dynamics of dissociation attachment via the two lowest energy Feshbach resonances. The combination of momentum imaging experiments and theory can reveal dissociation dynamics for which the axial recoil approximation breaks down and thus provides a powerful reaction microscope for DEA to polyatomics.

  18. Applying a Trochoidal Electron Monochromator in Dissociative Electron Attachment Scattering

    NASA Astrophysics Data System (ADS)

    Arreola, Esmeralda

    2016-03-01

    Since the pioneering work of Boudiaffa et al., it has been understood that electrons, even with energies near or below the ionization threshold, are capable of initiating strand-breaks in human DNA. This discovery raised important questions for cancer treatments, since sub-ionizing electrons are known to be the most copiously produced secondary product of radiation therapy. But even to date these factors are largely excluded from dosimetry calculations. This lack of inclusion is, at least in part, certainly due to the dearth of fundamental data describing low-energy electron interactions with nucleotide molecules that form the basis of DNA. Understanding of how such slow electrons are able to damage DNA remains incomplete, but the strongly peaked nature of Boudiaffa et al.'s data gives strong hints at resonantly driven collision processes. DNA damage is therefore most likely driven by ``dissociative electron attachment'' (DEA). DEA is a rather complicated process to model due to the coupling of electronic and nuclear degrees of freedom in the molecule. At the California State University Fullerton, we are currently commissioning a new spectrometer to study dissociation channels, reaction rates and orientation effects in DEA collisions between slow electrons and nucleotide molecules. At the meeting we will present design parameters and commissioning data for this new apparatus.

  19. Upper critical field, pressure-dependent superconductivity and electronic anisotropy of Sm4Fe2As2Te(1-x)O(4-y)F(y).

    PubMed

    Pisoni, A; Katrych, S; Szirmai, P; Náfrádi, B; Gaál, R; Karpinski, J; Forró, L

    2016-03-23

    We present a detailed study of the electrical transport properties of a recently discovered iron-based superconductor: Sm4Fe2As2Te0.72O2.8F1.2. We followed the temperature dependence of the upper critical field by resistivity measurement of single crystals in magnetic fields up to 16 T, oriented along the two main crystallographic directions. This material exhibits a zero-temperature upper critical field of 90 T and 65 T parallel and perpendicular to the Fe2As2 planes, respectively. An unprecedented superconducting magnetic anisotropy γH=H(c2)(ab)/H(c2)(c) ~ 14 is observed near Tc, and it decreases at lower temperatures as expected in multiband superconductors. Direct measurement of the electronic anisotropy was performed on microfabricated samples, showing a value of ρ(c)/ρ(ab)(300K) ~ 5 that rises up to 19 near Tc . Finally, we have studied the pressure and temperature dependence of the in-plane resistivity. The critical temperature decreases linearly upon application of hydrostatic pressure (up to 2 GPa) similarly to overdoped cuprate superconductors. The resistivity shows saturation at high temperatures, suggesting that the material approaches the Mott-Ioffe-Regel limit for metallic conduction. Indeed, we have successfully modelled the resistivity in the normal state with a parallel resistor model that is widely accepted for this state. All the measured quantities suggest strong pressure dependence of the density of states. PMID:26895190

  20. BEHAVIOR OF EXCESS ELECTRONS IN SUPERCRITICAL FLUIDS - ELECTRON ATTACHMENT

    SciTech Connect

    NISHIKAWA,M.; HOLROYD,R.A.; ITOH,K.

    1999-07-01

    The behavior of excess electrons in supercritical ethane was investigated by measuring mobility and reaction rates. Mobilities were measured by means of a time-of-flight method at 306--320K as a function of pressure. Mobility values decreased at all temperatures with increasing pressure, but showed a small minimum or a shoulder at the pressure where the compressibility {chi}{sub T} has a peak. Electron attachment to CO{sub 2}, NO, pyrimidine and C{sub 2}F{sub 4} over the same temperature range was studied as a function of pressure. Both attachment rate constants k{sub a} for NO and C{sub 2}F{sub 4}, and equilibrium constants K({double_bond}k{sub a}/k{sub d}) for CO{sub 2} and pyrimidine increased sharply at pressures of {chi}{sub T} peaks. Activation volumes V{sub a}* and reaction volumes {Delta}V{sub r} are very large and negative in the critical region. The volume change is mainly due to electrostriction around ions formed. The results are compared to volume changes predicted by, a compressible continuum model.

  1. Upper critical field, pressure-dependent superconductivity and electronic anisotropy of Sm4Fe2As2Te1-x O4-y F y

    NASA Astrophysics Data System (ADS)

    Pisoni, A.; Katrych, S.; Szirmai, P.; Náfrádi, B.; Gaál, R.; Karpinski, J.; Forró, L.

    2016-03-01

    We present a detailed study of the electrical transport properties of a recently discovered iron-based superconductor: Sm4Fe2As2Te0.72O2.8F1.2. We followed the temperature dependence of the upper critical field by resistivity measurement of single crystals in magnetic fields up to 16 T, oriented along the two main crystallographic directions. This material exhibits a zero-temperature upper critical field of 90 T and 65 T parallel and perpendicular to the Fe2As2 planes, respectively. An unprecedented superconducting magnetic anisotropy {γH}=Hc2ab/Hc2c˜ 14 is observed near T c , and it decreases at lower temperatures as expected in multiband superconductors. Direct measurement of the electronic anisotropy was performed on microfabricated samples, showing a value of {ρc}/{ρab}≤ft(300 \\text{K}\\right)˜ 5 that rises up to 19 near T c . Finally, we have studied the pressure and temperature dependence of the in-plane resistivity. The critical temperature decreases linearly upon application of hydrostatic pressure (up to 2 GPa) similarly to overdoped cuprate superconductors. The resistivity shows saturation at high temperatures, suggesting that the material approaches the Mott-Ioffe-Regel limit for metallic conduction. Indeed, we have successfully modelled the resistivity in the normal state with a parallel resistor model that is widely accepted for this state. All the measured quantities suggest strong pressure dependence of the density of states.

  2. Dissociative attachment reactions of electrons with gas phase superacids

    SciTech Connect

    Liu, X.

    1992-01-01

    Using the flowing afterglow Langmuir probe (FALP) technique, dissociative attachment coefficients [beta] for reactions of electrons with gas phase superacids HCo(PF[sub 3])[sub 4], HRh(PF[sub 3])[sub 4] and carbonyl hydride complexes HMn(CO)[sub 5], HRe(CO)[sub 5] have been determined under thermal conditions over the approximate temperature range 300[approximately]550 K. The superacids react relatively slowly (<1/20 of [beta][sub max]) with free electrons in a thermal plasma, and the values of [beta] obtained this far do not show a correlation between acidity and [beta]. The pioneer researchers in this field had speculated that any superacid would be a rapid attacher of electrons; it was found that this speculation is not true in general. The product distribution of electron attachment reaction to HCo(PF[sub 3])[sub 4] was found to be independent of temperature even though the [beta][HCo(PF[sub 3])[sub 4

  3. Electron attachment to chlorine azide at 298 and 400 K

    SciTech Connect

    Freel, Keith; Friedman, Jeffrey F.; Miller, Thomas M.; Viggiano, A. A.; Heaven, Michael C.

    2010-04-07

    Electron attachment to chlorine azide (ClN{sub 3}) was studied using a flowing-afterglow Langmuir-probe apparatus. Electron attachment rates were measured to be 3.5x10{sup -8} and 4.5x10{sup -8} cm{sup 3} s{sup -1} at 298 and 400 K, respectively, with an estimated 35% absolute accuracy. Cl{sup -} was the sole ion product of the attachment reaction; weak ion signals were observed for other anions and attributed to impurities and secondary ion-molecule reactions. Assuming a relative uncertainty of {+-}10% for these data, an activation energy for the attachment reaction may be given as 24{+-}10 meV.

  4. Electron attachment to the phthalide molecule

    SciTech Connect

    Asfandiarov, N. L.; Pshenichnyuk, S. A.; Vorob’ev, A. S.; Nafikova, E. P.; Lachinov, A. N.; Kraikin, V. A.; Modelli, A.

    2015-05-07

    Phthalide, the simplest chain of conductive polymer thin film, was investigated by means of Electron Transmission Spectroscopy, Negative Ion Mass Spectrometry, and density functional theory quantum chemistry. It has been found that formation of gas-phase long-lived molecular anions of phthalide around 0.7 eV takes place through cleavage of a C–O bond of the pentacyclic ring of the parent molecular anion to give a vibrationally excited (electronically more stable) open-ring molecular anion. The energy of the transition state for ring opening of the parent negative ion is calculated to be 0.65 eV above the neutral ground state of the molecule. The energy (2.64 eV) evaluated for the corresponding transition state in the neutral molecule is much higher, so that the process of electron detachment from the anion must lead to a neutral molecule with its initial pentacyclic structure. The average lifetime of the molecular negative ions formed at an electron energy of 0.75 eV and 80 °C is measured to be about 100 μs. The known switching effect of thin phthalide films could stem from the presence of a similar open/closed transition state also in the polymer.

  5. Dissociative Attachment Reactions of Electrons with Gas Phase Superacids

    NASA Astrophysics Data System (ADS)

    Liu, Xifan

    Using the flowing afterglow Langmuir probe (FALP) technique, dissociative attachment coefficients beta for reactions of electrons with gas phase superacids HCo(PF_3)_4, HRh(PF _3)_4 and carbonyl hydride complexes HMn(CO)_5, HRe(CO) _5 have been determined under thermal conditions over the approximate temperature range 300~ 550 K. The superacids react relatively slowly (< 1/20 of beta_{rm max}) with free electrons in a thermal plasma, and the values of beta obtained this far do not show a correlation between acidity and beta. The pioneer researchers in this field had speculated that any superacid would be a rapid attacher of electrons; we found that this speculation is not true in general. The product distribution of electron attachment reaction to HCo(PF_3)_4 was found to be independent of temperature even though the beta (HCo(PF_3)_4 ) increases with temperature. This leads us to propose that the electron attachment process occurs well before the excited complex dissociates. In addition, the activation energy of HCo(PF_3)_4 for electron attachment has been derived from the Arrhenius plots. The carbonyl hydride complexes, HMn(CO) _5 and HRe(CO)_5, react relatively rapidly (>1/4 of beta_{rm max}) with free electrons in thermal plasma. This indicates that these reactions cannot be significantly endothermic. Observation of rapid attachment for these non-superacids shows that the Mn-CO and Re-CO bonds are weaker than the Mn-H and Re-H bonds, respectively. Comparisons between the carbonyl and trifluorophosphine cases implies that fast electron capture is related more to the CO ligand than to the transition -metal species.

  6. Low energy electron attachment at sub-meV resolution

    NASA Astrophysics Data System (ADS)

    Kortyna, A.; Howe, P.-T.; Darrach, M.; Chutjian, A.

    2000-06-01

    Single-photon ionization of rare-gas atoms is used to produce low energy electrons for the study of electron attachment to SF_6. Vacuum ultraviolet laser radiation (λ ≈ 92 nm), produced by nonlinear up-conversion techniques and tunable near the Xe^+ ^2P^0_1/2 threshold, intersects a Xe beam to yield photoelectrons that scatter from SF6 target molecules admixed into the same beam. The photoelectron energy, ɛ, is scanned over the range 0 <= ɛ <= 84 meV. A Monte Carlo model of the attachment signal shows that the electron energy distribution width is <100 μeV and that the electron attachment cross section below 5 meV obeys the expected ɛ-1/2 energy dependence without the need to modify the Wigner threshold law. At ɛ = 45 ± 1 meV, a resonant structure reveals the opening of an inelastic attachment channel associated with the ω6 vibrational mode of SF6 whose excitation energy has been measured previously to be 44.0 ± 0.2 meV. Further investigations into the threshold behavior of the electron attachment cross section are underway. This work was carried out at JPL/Caltech and supported through agreement with NASA.

  7. Reversal electron attachment ionizer for detection of trace species

    NASA Technical Reports Server (NTRS)

    Bernius, Mark T. (Inventor); Chutjian, Ara (Inventor)

    1990-01-01

    An in-line reversal electron, high-current ionizer capable of focusing a beam of electrons to a reversal region and executing a reversal of said electrons, such that the electrons possess zero kinetic energy at the point of reversal, may be used to produce both negative and positive ions. A sample gas is introduced at the point of electron reversal for low energy electron-(sample gas) molecule attachment with high efficiency. The attachment process produces negative ions from the sample gas, which includes species present in trace (minute) amounts. These ions are extracted efficiently and directed to a mass analyzer where they may be detected and identified. The generation and detection of positive ions is accomplished in a similar fashion with minimal adjustment to potentials applied to the apparatus.

  8. Dissociative Electron Attachment to Anthralin to Model Its Biochemical Reactions.

    PubMed

    Pshenichnyuk, Stanislav A; Komolov, Alexei S

    2014-08-21

    The antipsoriatic drug anthralin (dithranol) is known to be extensively accumulated inside mitochondria of keratinocytes and to interact with the electron flow of the respiratory chain. Primary products of the one-electron reduction of polyphenolic anthralin observed in vivo are its dehydrogenated anions, which are formed by H-atom abstraction. The same species are mainly generated at low electron energies by dissociative electron attachment (DEA) to anthralin molecules in vacuo. A likely mechanism for the biochemical transformations of anthralin under reductive conditions in vivo is hypothesized on the basis of its DEA properties. The involvement of excited electronic states generated by ultraviolet irradiation of skin is discussed. PMID:26278099

  9. Electron attachment and ion mobility in hydrocarbons and related systems

    SciTech Connect

    Bakale, G.

    1988-01-01

    During the last two decades, a firm base for the emerging field of liquid state electronics (LSE) has developed through studies of the transport and reaction properties of excess electrons in a variety of liquid-phase systems. Pulse-conductivity techniques were used in many of these studies to measure the mobilities of electrons and ions in pure liquids as well as the rate constants of electron attachment to a wide variety of electron-accepting solutes. Results obtained through such studies have interdisciplinary implications that are described in the discussion that follows which includes examples of the contributions of LSE to physics, chemistry and biology. 42 refs.

  10. Electron attachment to the SF{sub 6} molecule

    SciTech Connect

    Smirnov, B. M. Kosarim, A. V.

    2015-09-15

    Various models for transition between electron and nuclear subsystems are compared in the case of electron attachment to the SF{sub 6} molecule. Experimental data, including the cross section of electron attachment to this molecule as a function of the electron energy and vibrational temperature, the rate constants of this process in swarm experiments, and the rates of the chemionization process involving Rydberg atoms and the SF{sub 6} molecule, are collected and treated. Based on the data and on the resonant character of electron capture into an autodetachment ion state in accordance with the Breit–Wigner formula, we find that intersection of the molecule and negative ion electron terms proceeds above the potential well bottom of the molecule with the barrier height 0.05–0.1 eV, and the transition between these electron terms has both the tunnel and abovebarrier character. The limit of small electron energies e for the electron attachment cross section at room vibrational temperature takes place at ε ≪ 2 meV, while in the range 2 meV ≪ ε ≪ 80 meV, the cross section is inversely proportional to ε. In considering the attachment process as a result of the interaction between the electron and vibrational degrees of freedom, we find the coupling factor f between them to be f = aT at low vibrational temperatures T with a ≈ 3 × 10{sup −4} K{sup −1}. The coupling factor is independent of the temperature at T > 400 K.

  11. Electron Attachment Studies for CHCl3 Using Ion Mobility Spectrometry

    NASA Astrophysics Data System (ADS)

    Han, Hai-yan; Feng, Hong-tao; Li, Hu; Wang, Hong-mei; Jiang, Hai-he; Chu, Yan-nan

    2011-04-01

    The dissociative electron attachment process for CHCl3 at different electric field have been studied with nitrogen as drift and carrier gas using corona discharge ionization source ion mobility spectrometry (CD-IMS). The corresponding electron attachment rate constants varied from 1.26×10-8 cm3/(molecules s) to 8.24×10-9 cm3/(molecules s) as the electric field changed from 200 V/cm to 500 V/cm. At a fixed electric field in the drift region, the attachment rate constants are also detected at different sample concentration. The ion-molecule reaction rate constants for the further reaction between Cl- and CHCl3 are also detected, which indicates that the technique maybe becomes a new method to research the rate constants between ions and neural molecules. And the reaction rate constants between Cl- and CHCl3 are the first time detected using CD-IMS.

  12. Dissociative electron attachment to the radiosensitizing chemotherapeutic agent hydroxyurea.

    PubMed

    Huber, S E; Śmiałek, M A; Tanzer, K; Denifl, S

    2016-06-14

    Dissociative electron attachment to hydroxyurea was studied in the gas phase for electron energies ranging from zero to 9 eV in order to probe its radiosensitizing capabilities. The experiments were carried out using a hemispherical electron monochromator coupled with a quadrupole mass spectrometer. Diversified fragmentation of hydroxyurea was observed upon low energy electron attachment and here we highlight the major dissociation channels. Moreover, thermodynamic thresholds for various fragmentation reactions are reported to support the discussion of the experimental findings. The dominant dissociation channel, which was observed over a broad range of energies, is associated with formation of NCO(-), water, and the amidogen (NH2) radical. The second and third most dominant dissociation channels are associated with formation of NCNH(-) and NHCONH2 (-), respectively, which are both directly related to formation of the highly reactive hydroxyl radical. Other ions observed with significant abundance in the mass spectra were NH2 (-)/O(-), OH(-), CN(-), HNOH(-), NCONH2 (-), and ONHCONH2 (-). PMID:27306009

  13. Dissociative electron attachment to the radiosensitizing chemotherapeutic agent hydroxyurea

    NASA Astrophysics Data System (ADS)

    Huber, S. E.; Śmiałek, M. A.; Tanzer, K.; Denifl, S.

    2016-06-01

    Dissociative electron attachment to hydroxyurea was studied in the gas phase for electron energies ranging from zero to 9 eV in order to probe its radiosensitizing capabilities. The experiments were carried out using a hemispherical electron monochromator coupled with a quadrupole mass spectrometer. Diversified fragmentation of hydroxyurea was observed upon low energy electron attachment and here we highlight the major dissociation channels. Moreover, thermodynamic thresholds for various fragmentation reactions are reported to support the discussion of the experimental findings. The dominant dissociation channel, which was observed over a broad range of energies, is associated with formation of NCO-, water, and the amidogen (NH2) radical. The second and third most dominant dissociation channels are associated with formation of NCNH- and NHCONH2-, respectively, which are both directly related to formation of the highly reactive hydroxyl radical. Other ions observed with significant abundance in the mass spectra were NH2-/O-, OH-, CN-, HNOH-, NCONH2-, and ONHCONH2-.

  14. Inelastic electron interaction (attachment/ionization) with deoxyribose

    NASA Astrophysics Data System (ADS)

    Ptasińska, S.; Denifl, S.; Scheier, P.; Märk, T. D.

    2004-05-01

    We have investigated experimentally the formation of anions and cations of deoxyribose sugar (C5H10O4) via inelastic electron interaction (attachment/ionization) using a monochromatic electron beam in combination with a quadrupole mass spectrometer. The ion yields were measured as a function of the incident electron energy between about 0 and 20 eV. As in the case of other biomolecules (nucleobases and amino acids), low energy electron attachment leads to destruction of the molecule via dissociative electron attachment reactions. In contrast to the previously investigated biomolecules dehydrogenation is not the predominant reaction channel for deoxyribose; the anion with the highest dissociative electron attachment (DEA) cross section of deoxyribose is formed by the release of neutral particles equal to two water molecules. Moreover, several of the DEA reactions proceed already with "zero energy" incident electrons. In addition, the fragmentation pattern of positively charged ions of deoxyribose also indicates strong decomposition of the molecule by incident electrons. For sugar the relative amount of fragment ions compared to that of the parent cation is about an order of magnitude larger than in the case of nucleobases. We determined an ionization energy value for C5H10O4+ of 10.51±0.11 eV, which is in good agreement with ab initio calculations. For the fragment ion C5H6O2+ we obtained a threshold energy lower than the ionization energy of the parent molecular ion. All of these results have important bearing for the question of what happens in exposure of living tissue to ionizing radiation. Energy deposition into irradiated cells produces electrons as the dominant secondary species. At an early time after irradiation these electrons exist as ballistic electrons with an initial energy distribution up to several tens of electron volts. It is just this energy regime for which we find in the present study rather characteristic differences in the outcome of electron

  15. Dissociative electron attachment to titatinum tetrachloride and titanium tetraisopropoxide

    NASA Astrophysics Data System (ADS)

    Bjarnason, Elías H.; Ómarsson, Benedikt; Engmann, Sarah; Ómarsson, Frímann H.; Ingólfsson, Oddur

    2014-05-01

    Here we present a dissociative electron attachment study of titanium tetrachloride and titanium tetraisopropoxide in the incident electron energy range from about 0-18 eV. The results are compared to electron impact ionization and fragmentation of these compounds and discussed in relation to the role of secondary electrons in focused electron beam induced deposition. We also use the opportunity and describe in detail a recently constructed crossed beam apparatus for the study of the energy dependency of ion formation in low energy electron interaction with gas phase molecules. Contribution to the Topical Issue "Electron and Positron Induced Processes", edited by Michael Brunger, Radu Campeanu, Masamitsu Hoshino, Oddur Ingólfsson, Paulo Limão-Vieira, Nigel Mason, Yasuyuki Nagashima and Hajime Tanuma.

  16. Electron attachment and positive ion chemistry of monohydrogenated fluorocarbon radicals

    NASA Astrophysics Data System (ADS)

    Wiens, Justin P.; Shuman, Nicholas S.; Miller, Thomas M.; Viggiano, Albert A.

    2015-08-01

    Rate coefficients and product branching fractions for electron attachment and for reaction with Ar+ are measured over the temperature range 300-585 K for three monohydrogenated fluorocarbon (HFC) radicals (CF3CHF, CHF2CF2, and CF3CHFCF2), as well as their five closed-shell precursors (1-HC2F4I, 2-HC2F4I, 2-HC2F4Br, 1-HC3F6I, 2-HC3F6Br). Attachment to the HFC radicals is always fairly inefficient (between 0.1% and 10% of the Vogt-Wannier capture rate), but generally faster than attachment to analogous perfluorinated carbon radicals. The primary products in all cases are HF-loss to yield CnFm-1- anions, with only a minor branching to F- product. In all cases the temperature dependences are weak. Attachment to the precursor halocarbons is near the capture rate with a slight negative temperature dependence in all cases except for 2-HC2F4Br, which is ˜10% efficient at 300 K and becomes more efficient, approaching the capture rate at higher temperatures. All attachment kinetics are successfully reproduced using a kinetic modeling approach. Reaction of the HFC radicals with Ar+ proceeds at or near the calculated collisional rate coefficient in all cases, yielding a wide variety of product ions.

  17. Radiative electronic attachment to molecules of astrophysical interest

    NASA Astrophysics Data System (ADS)

    Douguet, Nicolas; Kokoouline, Viatcheslav; Fonseca Dos Santos, Samantha; Dulieu, Olivier; Raoult, Maurice; Orel, Ann

    2013-05-01

    We have developed a first-principles approach to study the process of radiative electron attachment (REA) to linear molecules of astrophysical interest Mol +e- --> Mol- + ℏω (Mo l- = CnH-, CnN-). The approach is based on accurate ab initio calculations of electronic bound and continuum states of the negative ion, obtained through the complex Kohn variational method. We present our benchmark calculation for the formation of the simplest observed ion CN- by REA, as well as our preliminary results for the formation of C3N- and C4H- by REA. We calculated a low rate of 10-15cm3 / s at 30 K for CN- and rates about 20 time larger for C3N- and C4H- due to larger transition dipole moments. These two latter ions possess dipole states and we have also considered their potential role in the process of radiative electronic attachment. Finally, our results suggest that the negative molecular ions, recently observed in the interstellar medium, can hardly be formed by the process of radiative electron attachment. This work is supported by the DOE Office of Basic Energy Science and the National Science Foundation, Grant No's PHY-10-68785 and PHY-11-60611.

  18. Wide temperature range electronic device with lead attachment

    NASA Technical Reports Server (NTRS)

    Farrell, R. (Inventor)

    1973-01-01

    A electronic device including lead attachment structure which permits operation of the devices over a wide temperature range is reported. The device comprises a core conductor having a thin coating of metal thereon whereby only a limited amount of coating material is available to form an alloy which bonds the core conductor to the device electrode, the electrode composition thus being affected only in the region adjacent to the lead.

  19. Ultralow Energy Electron Attachment at Sub-Millielectron Volt Resolution

    NASA Technical Reports Server (NTRS)

    Chutjian, A.; Kortyna, A.; Darrach, M. R.; Howe, P. -T.

    1999-01-01

    The technique of rare-gas photoionization has been extended by use of direct laser ionization to electron energies epsilon in the range 0-100 meV, with a resolution Delta(epsilon) of 0.4-0.5 meV (FWHM). Tunable UV light at (Lambda)276 nm is produced using a pulsed Nd:YAG laser and nonlinear mixing techniques. The beam is frequency tripled in a pulsed jet of xenon. The VUV radiation, tunable at (Lambda)92 nm, is then used to photoionize Xe at its 2P(sub 1/2) threshold (single-photon ionization). The photoelectrons produced interact with admixed target gas to generate negative ions through the s-wave capture process. Recent results in electron attachment to SF(sub 6) will be reported which show resonance structure at the opening of the ground-state vibrational channels. This structure corresponds to the process of vibrational excitation + attachment, which is superimposed on the underlying s-wave (direct) capture process. It should be a general phenomenon, present in a wide variety of zero-energy electron attaching molecules.

  20. Dissociative attachment reactions of electrons with strong acid molecules

    NASA Astrophysics Data System (ADS)

    Adams, Nigel G.; Smith, David; Viggiano, A. A.; Paulson, John F.; Henchman, Michael J.

    1986-06-01

    Using the flowing afterglow/Langmuir probe (FALP) technique, we have determined (at variously 300 and 570 K) the dissociative attachment coefficients β for the reactions of electrons with the common acids HNO3 (producing NO-2) and H2SO4 (HSO-4), the superacids FSO3H (FSO-3), CF3SO3H (CF3SO-3), ClSO3H (ClSO-3,Cl-), the acid anhydride (CF3SO2)2O (CF3SO-3), and the halogen halides HBr (Br-) and HI (I-). The anions formed in the reactions are those given in the parentheses. The reactions with HF and HCl were investigated, but did not occur at a measurable rate since they are very endothermic. Dissociative attachment is rapid for the common acids, the superacids, and the anhydride, the measured β being appreciable fractions of the theoretical maximum β for such reactions, βmax. The HI reaction is very fast ( β˜βmax) but the HBr reaction occurs much more slowly because it is significantly endothermic. The data indicate that the extreme acidity of the (Bronsted-type) superacids has its equivalence in the very efficient gas-phase dissociative attachment which these species undergo when reacting with free electrons. The anions of the superacids generated in these reactions, notably FSO-3 and CF3SO-3, are very stable (unreactive) implying exceptionally large electron affinities for the FSO3 and CF3SO3 radicals.

  1. Ultralow Energy Electron Attachment at Sub-Millielectron Volt Resolution

    NASA Astrophysics Data System (ADS)

    Chutjian, Ara

    1999-10-01

    The technique of rare-gas photoionization(J. M. Ajello and A. Chutjian, J. Chem. Phys. 65), 5524 (1976). has been extended(A. Kortyna, M. Darrach and A. Chutjian, Bull. Am. Phys. Soc. 43), 1336 (1998). by use of direct laser ionization to electron energies ɛ in the range 0-100 meV, with a resolution Δɛ of 0.4-0.5 meV (FWHM). Tunable UV light at λ276 nm is produced using a pulsed Nd:YAG laser and nonlinear mixing techniques. The beam is frequency tripled in a pulsed jet of xenon. The VUV radiation, tunable at λ92 nm, is then used to photoionize Xe at its ^2P_1/2 threshold (single-photon ionization). The photoelectrons produced interact with admixed target gas to generate negative ions through the s-wave capture process. Recent results in electron attachment to SF6 will be reported which show resonance structure at the opening of the ground-state vibrational channels.^3,(H. Hotop et al., AIP Conf. Proc. Ser. 360 (AIP, New York, 1995), and private communication.) This structure corresponds to the process of vibrational excitation + attachment, which is superimposed on the underlying s-wave (direct) capture process. It should be a general phenomenon, present in a wide variety of zero-energy electron attaching molecules.

  2. Dissociative attachment of electrons with Si2H6

    NASA Technical Reports Server (NTRS)

    Krishnakumar, E.; Srivastava, S. K.; Iga, I.

    1991-01-01

    Cross-sections for the production of negative ion fragments by electron attachment to Si2H6 and ion pair formation from it have been measured by utilizing the crossed electron beam-molecular beam collision technique. The negative ions are mass-analyzed by employing a quadrupole mass spectrometer. There are serious disagreements between the present and two previously published results. In the present paper cross-section values, appearance potentials, and the various channels of dissociation for the formation of negative monosilane fragments are presented.

  3. Ionization, electron attachment, and drift in CHF3.

    PubMed

    de Urquijo, J; Alvarez, I; Cisneros, C

    1999-10-01

    Using a pulsed Townsend technique, we have measured the effective ionization coefficient and the electron drift velocities in CHF(3). The density-normalized electric field intensity E/N ranged from 4 to 250 townsends (Td) (1 Td=10(-17) V cm(2)). The E/N value at which the effective ionization coefficient becomes zero was estimated to be 66 Td. For E/N<20 Td, the electron attachment coefficients are practically constant, and are compatible to within about +/-70% with previously measured values at thermal energies and above. PMID:11970373

  4. Electron attachment to antipyretics: Possible implications of their metabolic pathways

    NASA Astrophysics Data System (ADS)

    Pshenichnyuk, Stanislav A.; Modelli, Alberto

    2012-06-01

    The empty-level structures and formation of negative ion states via resonance attachment of low-energy (0-15 eV) electrons into vacant molecular orbitals in a series of non-steroidal anti-inflammatory drugs (NSAIDs), namely aspirin, paracetamol, phenacetin, and ibuprofen, were investigated in vacuo by electron transmission and dissociative electron attachment (DEA) spectroscopies, with the aim to model the behavior of these antipyretic agents under reductive conditions in vivo. The experimental findings are interpreted with the support of density functional theory calculations. The negative and neutral fragments formed by DEA in the gas phase display similarities with the main metabolites of these commonly used NSAIDs generated in vivo by the action of cytochrome P450 enzymes, as well as with several known active agents. It is concluded that xenobiotic molecules which possess pronounced electron-accepting properties could in principle follow metabolic pathways which parallel the gas-phase dissociative decay channels observed in the DEA spectra at incident electron energies below 1 eV. Unwanted side effects as, e.g., hepatoxicity or carcinogenicity produced by the NSAIDs under study in human organism are discussed within the "free radical model" framework, reported earlier to describe the toxic action of the well-known model toxicant carbon tetrachloride.

  5. Electron attachment to antipyretics: possible implications of their metabolic pathways.

    PubMed

    Pshenichnyuk, Stanislav A; Modelli, Alberto

    2012-06-21

    The empty-level structures and formation of negative ion states via resonance attachment of low-energy (0-15 eV) electrons into vacant molecular orbitals in a series of non-steroidal anti-inflammatory drugs (NSAIDs), namely aspirin, paracetamol, phenacetin, and ibuprofen, were investigated in vacuo by electron transmission and dissociative electron attachment (DEA) spectroscopies, with the aim to model the behavior of these antipyretic agents under reductive conditions in vivo. The experimental findings are interpreted with the support of density functional theory calculations. The negative and neutral fragments formed by DEA in the gas phase display similarities with the main metabolites of these commonly used NSAIDs generated in vivo by the action of cytochrome P450 enzymes, as well as with several known active agents. It is concluded that xenobiotic molecules which possess pronounced electron-accepting properties could in principle follow metabolic pathways which parallel the gas-phase dissociative decay channels observed in the DEA spectra at incident electron energies below 1 eV. Unwanted side effects as, e.g., hepatoxicity or carcinogenicity produced by the NSAIDs under study in human organism are discussed within the "free radical model" framework, reported earlier to describe the toxic action of the well-known model toxicant carbon tetrachloride. PMID:22779593

  6. Electron attachment and positive ion chemistry of monohydrogenated fluorocarbon radicals

    SciTech Connect

    Wiens, Justin P.; Shuman, Nicholas S.; Miller, Thomas M.; Viggiano, Albert A.

    2015-08-21

    Rate coefficients and product branching fractions for electron attachment and for reaction with Ar{sup +} are measured over the temperature range 300–585 K for three monohydrogenated fluorocarbon (HFC) radicals (CF{sub 3}CHF, CHF{sub 2}CF{sub 2}, and CF{sub 3}CHFCF{sub 2}), as well as their five closed-shell precursors (1-HC{sub 2}F{sub 4}I, 2-HC{sub 2}F{sub 4}I, 2-HC{sub 2}F{sub 4}Br, 1-HC{sub 3}F{sub 6}I, 2-HC{sub 3}F{sub 6}Br). Attachment to the HFC radicals is always fairly inefficient (between 0.1% and 10% of the Vogt–Wannier capture rate), but generally faster than attachment to analogous perfluorinated carbon radicals. The primary products in all cases are HF-loss to yield C{sub n}F{sub m−1}{sup −} anions, with only a minor branching to F{sup −} product. In all cases the temperature dependences are weak. Attachment to the precursor halocarbons is near the capture rate with a slight negative temperature dependence in all cases except for 2-HC{sub 2}F{sub 4}Br, which is ∼10% efficient at 300 K and becomes more efficient, approaching the capture rate at higher temperatures. All attachment kinetics are successfully reproduced using a kinetic modeling approach. Reaction of the HFC radicals with Ar{sup +} proceeds at or near the calculated collisional rate coefficient in all cases, yielding a wide variety of product ions.

  7. Low-energy dissociative electron attachment to CF2

    NASA Astrophysics Data System (ADS)

    Chourou, S. T.; Larson, Ã.; Orel, A. E.

    2015-08-01

    We present the results of a theoretical study of dissociative electron attachment (DEA) of low-energy electrons to CF2. We carried out electron scattering calculations using the complex Kohn variational method at the static-exchange and relaxed self-consistent field (SCF) level at the equilibrium geometry and compare our differential cross sections to other results. We then repeated these calculations as a function of the three internal degrees of freedom to obtain the resonance energy surfaces and autoionization widths. We use this data as input to form the Hamiltonian relevant to the nuclear dynamics. The multidimensional wave equation is solved using the multiconfiguration time-dependent Hartree (MCTDH) approach within the local approximation.

  8. Revealing Dissociative Electron Attachment Dynamics in Polyatomic Molecules Using Momentum Imaging Experiments and Electron Scattering Calculations

    NASA Astrophysics Data System (ADS)

    Belkacem, Ali; Slaughter, Daniel

    2015-05-01

    Understanding electron-driven chemical reactions is important for improving a variety of technological applications such as materials processing and the important role they play in the radiation damage in bulk matter. Furthermore, dissociative electron attachment often exhibits site-selective bond cleavage, which holds promise for prediction and precise control of electron-driven chemical reactions. Recent dynamical studies of these reactions have demonstrated that an understanding of anion dissociation dynamics beyond simple one-dimensional models is crucial in interpreting the measured fragment angular distributions. We combine ion fragment momentum imaging experiments with electron attachment entrance amplitude calculations to interrogate the non-Born-Oppenheimer dynamics of dissociative electron attachment in polyatomic molecules. We will report recent experimental developments in molecules of technological interest including methanol, methane and uracil. Work supported by Chemical Sciences, Geosciences and Biosciences division of BES/DOE.

  9. Pressure dependence of the conduction-electron-spin-resonance linewidth of the α and β phases of di-bis(ethylene- diothiolo)tetrathiafulvalene triiodide

    NASA Astrophysics Data System (ADS)

    Forró, L.; Sekretarczyk, G.; Krupski, M.; Schweitzer, D.; Keller, H.

    1987-02-01

    We report conduction-electron-spin-resonance linewidth (ΔH) measurements of the α and β phases of the organic conductor di-bis(ethylenediothiolo)tetrathiafulvalene triiodide [(BEDT-TTF)2I3] in the 80-300 K temperature range under applied pressures of up to 5 kbar. ΔH increases under pressure in contrast to the predictions of the Elliot formula for the spin relaxation in metals. The pressure derivative d(lnΔH)/dP is -5.5+/-1%/kbar and 9.8+/-1%/kbar for the α and β phases of (BEDT-TTF)2I3 respectively.

  10. Pressure dependence of the electronic structure of a [311] piezoelectric Ga0.85In0.15As/AlAs superlattice

    NASA Astrophysics Data System (ADS)

    Reparaz, J. S.; Muniz, L. R.; Goñi, A. R.; Alonso, M. I.; Rozas, G.; Fainstein, A.; Saravanan, S.; Vaccaro, P. O.

    2010-09-01

    We have studied the electronic subband structure of a piezoelectric [311] Ga0.85In0.15As/AlAs superlattice by means of high-hydrostatic pressure and excitation-power-dependent photoluminescence at 78 K. In particular, we unraveled the origin of two optical transitions at around 1.96 and 2 eV at ambient pressure, which were recently found to give rise to an unexpectedly strong resonant enhancement of the acoustic-phonon Raman scattering for such samples with permanent built-in piezoelectric fields [G. Rozas , Phys. Rev. B 77, 165314 (2008)10.1103/PhysRevB.77.165314]. Here we demonstrate that these transitions are doubly indirect, in real and reciprocal space, corresponding to radiative recombination processes between electrons at the X valleys of the AlAs barriers and heavy holes at the Γ point of the Brillouin zone but confined to the GaInAs quantum wells. In addition, the partial screening of the piezoelectric field induced by carrier photoexcitation under illumination becomes largely suppressed for pressures above 1.1 GPa due to conduction-band Γ-X crossover effects.

  11. Dissociative electron attachment to gas-phase 5-bromouracil

    NASA Astrophysics Data System (ADS)

    Abdoul-Carime, H.; Huels, M. A.; Brüning, F.; Illenberger, E.; Sanche, L.

    2000-08-01

    We report measurements of dissociative electron attachment (DEA) to gaseous 5-bromouracil (BrU) for incident electron energies between 0 and 16 eV. Low energy electron impact on BrU leads not only to the formation of a long lived parent anion BrU-, but also various anion fragments resulting from endo- and exo-cyclic bond ruptures, such as Br-, uracil-yl anions, i.e., (U-yl)-, OCN-, and a 68 amu anion tentatively attributed to H2C3NO-. The incident electron energy dependent signatures of either the Br- and (U-yl)- yields (at 0, 1.4, and 6 eV), or the OCN- and H2C3NO- yields (at 1.6 and 5.0 eV) suggests competing DEA channels for anion fragment formation. The production cross sections, at 0 eV incident electron energy, for BrU-, Br-, and (U-yl)- are estimated to be about 6×10-15, 6×10-14, and 1.0×10-15 cm2, respectively.

  12. Dissociative electron attachment to the gas-phase nucleobase hypoxanthine

    SciTech Connect

    Dawley, M. Michele; Tanzer, Katrin; Denifl, Stephan E-mail: Sylwia.Ptasinska.1@nd.edu; Carmichael, Ian; Ptasińska, Sylwia E-mail: Sylwia.Ptasinska.1@nd.edu

    2015-06-07

    We present high-resolution measurements of the dissociative electron attachment (DEA) to isolated gas-phase hypoxanthine (C{sub 5}H{sub 4}N{sub 4}O, Hyp), a tRNA purine base. The anion mass spectra and individual ion efficiency curves from Hyp were measured as a function of electron energy below 9 eV. The mass spectra at 1 and 6 eV exhibit the highest anion yields, indicating possible common precursor ions that decay into the detectable anionic fragments. The (Hyp − H) anion (C{sub 5}H{sub 3}N{sub 4}O{sup −}) exhibits a sharp resonant peak at 1 eV, which we tentatively assign to a dipole-bound state of the keto-N1H,N9H tautomer in which dehydrogenation occurs at either the N1 or N9 position based upon our quantum chemical computations (B3LYP/6-311+G(d,p) and U(MP2-aug-cc-pVDZ+)) and prior studies with adenine. This closed-shell dehydrogenated anion is the dominant fragment formed upon electron attachment, as with other nucleobases. Seven other anions were also observed including (Hyp − NH){sup −}, C{sub 4}H{sub 3}N{sub 4}{sup −}/C{sub 4}HN{sub 3}O{sup −}, C{sub 4}H{sub 2}N{sub 3}{sup −}, C{sub 3}NO{sup −}/HC(HCN)CN{sup −}, OCN{sup −}, CN{sup −}, and O{sup −}. Most of these anions exhibit broad but weak resonances between 4 and 8 eV similar to many analogous anions from adenine. The DEA to Hyp involves significant fragmentation, which is relevant to understanding radiation damage of biomolecules.

  13. Isotope effect in dissociative electron attachment to HCN

    SciTech Connect

    Chourou, S. T.; Orel, A. E.

    2011-03-15

    We performed nuclear dynamics calculations on HCN and DCN to study the isotope effect in dissociative electron attachment. Our previous calculations at 333 K led to a ratio {sigma}{sup (CN-/HCN)}/{sigma}{sup (CN-/DCN)} of about 13, which is significantly higher than recent experimental findings. This discrepancy is attributed to the neglect of correlation and polarization effects in the scattering calculation performed. We carried out a relaxed-self-consistent field calculation to determine the variation of the resonance parameters under these effects. We observe a shift in the positions of the shape resonance as well as a narrowing of the autoionization widths resulting in an isotope ratio of 3.2 at T=333 K; in closer agreement with the measured value.

  14. Chiral Sensitivity in the Dissociative Electron Attachment of Halocamphor Molecules

    NASA Astrophysics Data System (ADS)

    Dreiling, Joan

    2016-05-01

    We have demonstrated chirally-dependent molecular destruction when incident longitudinally-spin-polarized (chiral) electrons break bonds in chiral molecules. This chiral sensitivity was observed through an asymmetry in the dissociative electron attachment (DEA) reaction rate with chiral 3-bromocamphor (C10 H15 BrO). Such an observation provides an unambiguous demonstration of the idea underlying the Vester-Ulbricht hypothesis, which attempts to explain the origins of the homochirality that is observed in many biological systems. While the lack of inversion symmetry in these reactions allows the effects we observe to occur, their dynamic causes are poorly understood. We have further studied the asymmetries in the DEA rates for two additional halocamphor molecules, 3-iodocamphor (C10 H15 IO) and 10-iodocamphor, in a systematic effort to illuminate the mechanisms responsible for the chiral sensitivity. The DEA signal depends on the sign of the incident electron helicity for a given target handedness in all molecules, and it varies with both the atomic number and the location of the heaviest atom in the molecule. Surprisingly, the DEA asymmetries for 10-iodocamphor, in which the heaviest atom is farther from a chiral center than for the other molecules, produced the largest asymmetries. This work was performed at the University of Nebraska-Lincoln. This project was funded by NSF Grant PHY-1206067.

  15. Ion Momentum Imaging of Dissociative Electron Attachment to Small Molecules

    NASA Astrophysics Data System (ADS)

    Fogle, Michael

    2015-09-01

    In recent years, low energy dissociative electron attachment (DEA) interactions have been of interest to varying biological and technological applications. To study the dynamics resulting from DEA, we used an ion-momentum imaging apparatus based on the Cold Target Recoil Ion Momentum Spectroscopy (COLTRIMS) technique in which a molecular beam is crossed by a pulsed electron beam. The beam interaction takes place in a 4 π pulsed electrostatic spectrometer that collects the anion fragments resulting from DEA. The molecular beam is formed by a supersonic expansion which results in a well-localized and cold target. Using this apparatus we have investigated the DEA dynamics for several small molecules: CO2 at the 4 eV shape resonance and the 8 eV Feshbach resonance; N2O at the 2.3 eV shape resonance; HCCH at the 3 eV shape resonance; and CF4 near the 7 eV resonance. An overview of these experimental ion-momentum results will be compared to ab initio electronic structure and fixed-nuclei scattering calculations to gauge the resulting dynamics driven by DEA. In many cases, conical intersections play a pivotal role in driving the dynamics. Some of these systems exhibit non-axial recoil conditions indicative of a bending dynamics in the transitory negative ion state while others exhibit a direct axial recoil dissociation without any bending. This work is supported by the National Science Foundation under Contract NSF-PHYS1404366.

  16. Precursor anion states in dissociative electron attachment to chlorophenol isomers

    NASA Astrophysics Data System (ADS)

    Kossoski, F.; Varella, M. T. do N.

    2016-07-01

    We report a theoretical study on low-energy (<10 eV) elastic electron scattering from chlorophenol isomers, namely, para-chlorophenol (pCP), meta-chlorophenol (mCP), and ortho-chlorophenol (oCP). The calculations were performed with the Schwinger multichannel method with pseudopotentials, and analysis of the computed integral cross sections and virtual orbitals revealed one σCCl ∗ , one σOH ∗ , and three π∗ shape resonances. We show that electron capture into the two lower lying π∗ orbitals initiates dissociative processes that lead to the elimination of the chloride ion, accounting for the two overlapping peaks where this fragment was observed. Despite the relatively small differences on the energetics of the π∗ resonances, a major isomeric effect was found on their corresponding autodetachment lifetimes, which accounts for the observed increasing cross sections in the progression pCP < mCP < oCP. In particular, dissociation from the π1 ∗ anion of pCP is largely suppressed because of the unfavorable mixing with the σCCl ∗ state. We found the intramolecular hydrogen bond present in oCP to have the opposite effects of stabilizing the σCCl ∗ resonance and destabilizing the σOH ∗ resonance. We also suggest that the hydrogen abstraction observed in chlorophenols and phenol actually takes place by a mechanism in which the incoming electron is directly attached to the dissociative σOH ∗ orbital.

  17. Electron-impact ionization and electron attachment cross sections of radicals important in transient gaseous discharges

    NASA Technical Reports Server (NTRS)

    Lee, Long C.; Srivastava, Santosh K.

    1990-01-01

    Electron-impact ionization and electron attachment cross sections of radicals and excited molecules were measured using an apparatus that consists of an electron beam, a molecular beam and a laser beam. The information obtained is needed for the pulse power applications in the areas of high power gaseous discharge switches, high energy lasers, particle beam experiments, and electromagnetic pulse systems. The basic data needed for the development of optically-controlled discharge switches were also investigated. Transient current pulses induced by laser irradiation of discharge media were observed and applied for the study of electron-molecule reaction kinetics in gaseous discharges.

  18. Precursor anion states in dissociative electron attachment to chlorophenol isomers.

    PubMed

    Kossoski, F; Varella, M T do N

    2016-07-28

    We report a theoretical study on low-energy (<10 eV) elastic electron scattering from chlorophenol isomers, namely, para-chlorophenol (pCP), meta-chlorophenol (mCP), and ortho-chlorophenol (oCP). The calculations were performed with the Schwinger multichannel method with pseudopotentials, and analysis of the computed integral cross sections and virtual orbitals revealed one σCCl (∗), one σOH (∗), and three π(∗) shape resonances. We show that electron capture into the two lower lying π(∗) orbitals initiates dissociative processes that lead to the elimination of the chloride ion, accounting for the two overlapping peaks where this fragment was observed. Despite the relatively small differences on the energetics of the π(∗) resonances, a major isomeric effect was found on their corresponding autodetachment lifetimes, which accounts for the observed increasing cross sections in the progression pCP < mCP < oCP. In particular, dissociation from the π1 (∗) anion of pCP is largely suppressed because of the unfavorable mixing with the σCCl (∗) state. We found the intramolecular hydrogen bond present in oCP to have the opposite effects of stabilizing the σCCl (∗) resonance and destabilizing the σOH (∗) resonance. We also suggest that the hydrogen abstraction observed in chlorophenols and phenol actually takes place by a mechanism in which the incoming electron is directly attached to the dissociative σOH (∗) orbital. PMID:27475364

  19. Study of Electron Transfer Processes between Simple Plasma Ions and Electron Attaching Gases

    NASA Astrophysics Data System (ADS)

    Williams, Ted; Adams, Nigel; Babcock, Lucia

    1998-11-01

    CCl4 and SF6 are gases that rapidly attach electrons. They are used in etchant plasmas and in high power switches to prevent breakdown. This attachment results in a simple negative ion chemistry that can be well characterized. A concurrent series of reactions involving positive ions also occurs, with ionization eventually being removed by ion-ion mutual neutralization. However, unlike the negative ion chemistry, the positive ion chemistry is more complex and has not been well characterized. Common plasma ions are those of the rare and diatomic gases, along with impurity ions such as H_2O^+ and H_3O^+. Reactions of these ions with CCl4 and SF6 generally occur rapidly by dissociative electron transfer. Some exceptions have been observed when the reactant ion contains an H-atom(s), such as the production of HCl when H_3^+ reacts with CCl_4. Since these reactions involve a fixed amount of energy, they bear similarity to photoelectron and photoelectron-photoion coincidence studies of these electron attaching gases in which only Franck-Condon transitions can occur. Comparision of product ions observed and rate coefficients gives better insights into the mechanism of the electron transfer process. Support by NSF AST-9415485 is gratefully acknowledged.

  20. Investigation of electron attachment in polyatomic molecules. Final report 1 Apr 77-31 Mar 80

    SciTech Connect

    Dowell, J.T.

    1980-05-30

    Electron attachment to polyatomic molecules was studied using molecular beams of variable temperature crossed with an electron of high energy resolution. Species investigated include sulfur hexafluoride, molybdenum hexafluoride, and tungsten oxide polymers. New results were obtained in sulfur hexafluoride demonstrating importance of internal energy for the dissociative attachment in molybdenum hexafluoride. Tungsten oxide vapor exhibits both monomer and dimer negative ion formation near zero energy, apparently from dissociative attachment to the trimer.

  1. Detection of explosives, nerve agents, and illicit substances by zero-energy electron attachment

    NASA Technical Reports Server (NTRS)

    Chutjian, A.; Darrach, M. R.

    2000-01-01

    The Reversal Electron Attachment Detection (READ) method, developed at JPL/Caltech, has been used to detect a variety of substances which have electron-attachment resonances at low and intermediate electron energies. In the case of zero-energy resonances, the cross section (hence attachment probability and instrument sensitivity) is mediated by the so-called s-wave phenomenon, in which the cross sections vary as the inverse of the electron velocity. Hence this is, in the limit of zero electron energy or velocity, one of the rare cases in atomic and molecular physics where one carries out detection via infinite cross sections.

  2. Obtaining electron attachment cross sections by means of linear inversion of swarm parameters

    NASA Astrophysics Data System (ADS)

    Rabie, M.; Haefliger, P.; Chachereau, A.; Franck, C. M.

    2015-02-01

    We investigate electron attachment to strongly attaching gases as a function of the electron energy. The total electron attachment cross section of this electronegative sample gas is determined from the effective ionization rate constant νeff/N measured in a swarm experiment using the buffer gases N2 and CO2 with minor proportions (≲0.8%) of the sample gas SF6, and C3F8 respectively. The measured rate constants νeff/N for varying reduced electric field strengths E/N are unfolded from the electron energy distribution of the buffer gases. Different unfolding routines for so-called ill-posed problems are tested to find robust solutions for the attachment cross section. Finally, we propose Tikhonov regularization, which is a well defined algorithm for discrete linear inversion problems, as most efficient. Our method gives rise to an approximate and clearly defined solution for the attachment cross section, and it is described in detail.

  3. Predictive a priori pressure-dependent kinetics.

    PubMed

    Jasper, Ahren W; Pelzer, Kenley M; Miller, James A; Kamarchik, Eugene; Harding, Lawrence B; Klippenstein, Stephen J

    2014-12-01

    The ability to predict the pressure dependence of chemical reaction rates would be a great boon to kinetic modeling of processes such as combustion and atmospheric chemistry. This pressure dependence is intimately related to the rate of collision-induced transitions in energy E and angular momentum J. We present a scheme for predicting this pressure dependence based on coupling trajectory-based determinations of moments of the E,J-resolved collisional transfer rates with the two-dimensional master equation. This completely a priori procedure provides a means for proceeding beyond the empiricism of prior work. The requisite microcanonical dissociation rates are obtained from ab initio transition state theory. Predictions for the CH4 = CH3 + H and C2H3 = C2H2 + H reaction systems are in excellent agreement with experiment. PMID:25477457

  4. A technique for the measurement of electron attachment to short-lived excited species

    SciTech Connect

    Christophorou, L.G.; Pinnaduwage, L.A. ); Bitouni, A.P. . Dept. of Physics)

    1990-01-01

    A technique is described for the measurement of electron attachment to short-lived ({approx lt}10{sup {minus}9} s) excited species. Preliminary results are presented for photoenhanced electron attachment to short-lived electronically-excited states of triethylamine molecules produced by laser two-photon excitation. The attachment cross sections for these excited states are estimated to be >10{sup {minus}11} cm{sup 2} and are {approximately}10{sup 7} larger compared to those for the unexcited (ground-state) molecules. 8 refs., 4 figs.

  5. Substrate dependence of electron-stimulated O - yields from dissociative electron attachment to physisorbed O2

    NASA Astrophysics Data System (ADS)

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

    1994-03-01

    We present measurements of O- electron stimulated desorption yields obtained under identical experimental conditions from 0.15 monolayers (ML) of O2 deposited onto disordered substrates consisting of 4 ML of either Kr, Xe, C2H6, C2H4, N2O, CH3Cl, or H2O, all condensed on Pt (polycrystalline). The resulting O- yield functions, for incident electron energies below 20 eV, are compared to that obtained from the O2/Kr solid; this allows us to assess the order of magnitude effects of the local substrate environment on dissociative electron attachment (DEA) via the 2Πu and gas phase forbidden 2Σ+g,u resonances of O-2. We note that, in addition to electron energy losses in the substrate prior to DEA to O2 and post-dissociation interactions of the O- with the substrate molecules, charge or energy transfer from the O-2 transient anion to a substrate molecule, and capture of the incident electron into a dissociative anion resonance of the substrate molecule may contribute to a reduced O- yield from the physisorbed O2. In the case of O2 deposited on amorphous ice, we find that the O- signal from DEA to O2 is completely absent for electron energies below 14 eV; we attribute this to a complete quenching of the dissociative O-2(2Πu, 2Σ+) resonances by the adjacent water molecules.

  6. Application of reversal electron attachment for ultrasensitive detection of thermal electron-attaching molecules - CCl4 and C6H5O2

    NASA Technical Reports Server (NTRS)

    Bernius, Mark T.; Chutjian, Ara

    1990-01-01

    A standard gas-dilution method was used to determine the selective response of the reversal electron attachment detector to carbon tetrachloride concentrations in nitrogen. Data are provided that determine the lowest concentration of sample detectable with the present instrumental configuration as being below 1.0 part per trillion by volume. The incorporation of a 90-deg electrostatic deflector with the quadrupole mass spectrometer is shown to be vital, and with it, negative-ion quadrupole mass spectrometry is used to characterize the ionization process. Observations are also made of the reversal electron attachment response to nitrobenzene. The analytical potential of reversal electron capture negative-ion mass spectrometry is examined, and areas for future development are discussed.

  7. High resolution threshold photoelectron spectroscopy by electron attachment

    NASA Technical Reports Server (NTRS)

    Chutjian, A.; Ajello, J. M. (Inventor)

    1979-01-01

    A system is provided for determining the stable energy levels of a species ion, of an atomic, molecular, or radical type, by application of ionizing energy of a predetermined level, such as through photoionization. The system adds a trapping gas to the gaseous species to provide a technique for detection of the energy levels. The electrons emitted from ionized species are captured by the trapping gas, only if the electrons have substantially zero kinetic energy. If the electrons have nearly zero energy, they are absorbed by the trapping gas to produce negative ions of the trapping gas that can be detected by a mass spectrometer. The applied energies (i.e. light frequencies) at which large quantities of trapping gas ions are detected, are the stable energy levels of the positive ion of the species. SF6 and CFCl3 have the narrowest acceptance bands, so that when they are used as the trapping gas, they bind electrons only when the electrons have very close to zero kinetic energy.

  8. Electron attachment to the interhalogens ClF, ICl, and IBr

    NASA Astrophysics Data System (ADS)

    Miller, T. M.; Wiens, J. P.; Sawyer, J. C.; Shuman, N. S.; Viggiano, A. A.; Khamesian, M.; Kokoouline, V.; Fabrikant, I. I.

    2016-05-01

    Electron attachment rate coefficients have been measured for the interhalogens ClF, ICl, and IBr over the range 300-900 K using a flowing-afterglow Langmuir-probe apparatus. The ClF case was also studied theoretically. ClF was found to attach electrons somewhat inefficiently with a rate coefficient of 7.5x 10-9 cm3/s at 300 K, doubling by 700 K. Even so, attachment to ClF is more efficient than seen earlier for F2 and Cl2, which brings up the interesting distinction that attachment to F2 and Cl2 is known to have p-wave threshold behavior, while in ClF the inversion symmetry is broken, allowing an s-wave component. The increase in the rate coefficient for attachment to ClF with temperature was found to be less pronounced than with F2 and Cl2. Ab initio potential energy curves were calculated for ClF and ClF-, and R-matrix theory was used to obtain the resonance widths and energies for the ground state curve crossing, which takes place near the equilibrium internuclear separation in ClF. A local complex potential model was used to calculate attachment cross sections and thermal rate coefficients. There is reasonable agreement between theory and experiment within the estimated 25% uncertainties in the data. Cl- is the only product ion from thermal electron attachment to ClF. Attachment to ICl is even less efficient by almost an order of magnitude than to ClF, namely, 9.5x 10-10 cm3/s at 300 K. Attachment to IBr is small enough that we place an upper limit of < 10-10 cm3/s at 300 K. Supported by AFOSR, DOE, and NSF.

  9. Note: Coherent resonances observed in the dissociative electron attachment to carbon monoxide

    SciTech Connect

    Wang, Xu-Dong; Xuan, Chuan-Jin; Tian, Shan Xi; Luo, Yi

    2015-08-14

    Succeeding our previous finding about coherent interference of the resonant states of CO{sup −} formed by the low-energy electron attachment [Tian et al. Phys. Rev. A 88, 012708 (2013)], here we provide further evidence of the coherent interference. The completely backward distributions of the O{sup −} fragment of the temporary CO{sup −} are observed with anion velocity map imaging technique in an electron energy range of 11.3–12.6 eV and explained as the results of the coherent interferences of three resonant states. Furthermore, the state configuration of the interference is changed with the increase of electron attachment energy.

  10. Higher-order equation-of-motion coupled-cluster methods for electron attachment

    NASA Astrophysics Data System (ADS)

    Kamiya, Muneaki; Hirata, So

    2007-04-01

    High-order equation-of-motion coupled-cluster methods for electron attachment (EA-EOM-CC) have been implemented with the aid of the symbolic algebra program TCE into parallel computer programs. Two types of size-extensive truncation have been applied to the electron-attachment and cluster excitation operators: (1) the electron-attachment operator truncated after the 2p-1h, 3p-2h, or 4p-3h level in combination with the cluster excitation operator after doubles, triples, or quadruples, respectively, defining EA-EOM-CCSD, EA-EOM-CCSDT, or EA-EOM-CCSDTQ; (2) the combination of up to the 3p-2h electron-attachment operator and up to the double cluster excitation operator [EA-EOM-CCSD(3p-2h)] or up to 4p-3h and triples [EA-EOM-CCSDT(4p-3h)]. These methods, capable of handling electron attachment to open-shell molecules, have been applied to the electron affinities of NH and C2, the excitation energies of CH, and the spectroscopic constants of all these molecules with the errors due to basis sets of finite sizes removed by extrapolation. The differences in the electron affinities or excitation energies between EA-EOM-CCSD and experiment are frequently in excess of 2eV for these molecules, which have severe multideterminant wave functions. Including higher-order operators, the EA-EOM-CC methods predict these quantities accurate to within 0.01eV of experimental values. In particular, the 3p-2h electron-attachment and triple cluster excitation operators are significant for achieving this accuracy.

  11. Higher-order equation-of-motion coupled-cluster methods for electron attachment.

    PubMed

    Kamiya, Muneaki; Hirata, So

    2007-04-01

    High-order equation-of-motion coupled-cluster methods for electron attachment (EA-EOM-CC) have been implemented with the aid of the symbolic algebra program TCE into parallel computer programs. Two types of size-extensive truncation have been applied to the electron-attachment and cluster excitation operators: (1) the electron-attachment operator truncated after the 2p-1h, 3p-2h, or 4p-3h level in combination with the cluster excitation operator after doubles, triples, or quadruples, respectively, defining EA-EOM-CCSD, EA-EOM-CCSDT, or EA-EOM-CCSDTQ; (2) the combination of up to the 3p-2h electron-attachment operator and up to the double cluster excitation operator [EA-EOM-CCSD(3p-2h)] or up to 4p-3h and triples [EA-EOM-CCSDT(4p-3h)]. These methods, capable of handling electron attachment to open-shell molecules, have been applied to the electron affinities of NH and C2, the excitation energies of CH, and the spectroscopic constants of all these molecules with the errors due to basis sets of finite sizes removed by extrapolation. The differences in the electron affinities or excitation energies between EA-EOM-CCSD and experiment are frequently in excess of 2 eV for these molecules, which have severe multideterminant wave functions. Including higher-order operators, the EA-EOM-CC methods predict these quantities accurate to within 0.01 eV of experimental values. In particular, the 3p-2h electron-attachment and triple cluster excitation operators are significant for achieving this accuracy. PMID:17430021

  12. Dissociative electron attachments to ethanol and acetaldehyde: A combined experimental and simulation study

    NASA Astrophysics Data System (ADS)

    Wang, Xu-Dong; Xuan, Chuan-Jin; Feng, Wen-Ling; Tian, Shan Xi

    2015-02-01

    Dissociation dynamics of the temporary negative ions of ethanol and acetaldehyde formed by the low-energy electron attachments is investigated by using the anion velocity map imaging technique and ab initio molecular dynamics simulations. The momentum images of the dominant fragments O-/OH- and CH3- are recorded, indicating the low kinetic energies of O-/OH- for ethanol while the low and high kinetic energy distributions of O- ions for acetaldehyde. The CH3- image for acetaldehyde also shows the low kinetic energy. With help of the dynamics simulations, the fragmentation processes are qualitatively clarified. A new cascade dissociation pathway to produce the slow O- ion via the dehydrogenated intermediate, CH3CHO- (acetaldehyde anion), is proposed for the dissociative electron attachment to ethanol. After the electron attachment to acetaldehyde molecule, the slow CH3- is produced quickly in the two-body dissociation with the internal energy redistributions in different aspects before bond cleavages.

  13. Electron attachment induced proton transfer in a DNA nucleoside pair: 2'-deoxyguanosine-2'-deoxycytidine.

    PubMed

    Gu, Jiande; Xie, Yaoming; Schaefer, Henry F

    2007-10-21

    To elucidate electron attachment induced damage in the DNA double helix, electron attachment to the 2'-deoxyribonucleoside pair dG:dC has been studied with the reliably calibrated B3LYP/DZP++ theoretical approach. The exploration of the potential energy surface of the neutral and anionic dG:dC pairs predicts a positive electron affinity for dG:dC [0.83 eV for adiabatic electron affinity (EAad) and 0.16 eV for vertical electron affinity (VEA)]. The substantial increases in the electron affinity of dG:dC (by 0.50 eV for EAad and 0.23 eV for VEA) compared to those of the dC nucleoside suggest that electron attachment to DNA double helices should be energetically favored with respect to the single strands. Most importantly, electron attachment to the dC moiety in the dG:dC pair is found to be able to trigger the proton transfer in the dG:dC- pair, surprisingly resulting in the lower energy distonic anionic complex d(G-H)-:d(C+H).. The negative charge for the latter system is located on the base of dC in the dG:dC- pair, while it is transferred to d(G-H) in d(G-H)-:d(C+H)., accompanied by the proton transfer from N1(dG) to N3(dC). The low energy barrier (2.4 kcal/mol) for proton transfer from dG to dC- suggests that the distonic d(G-H)-:d(C+H). pair should be one of the important intermediates in the process of electron attachment to DNA double helices. The formation of the neutral nucleoside radical d(C+H). is predicted to be the direct result of electron attachment to the DNA double helices. Since the neutral radical d(C+H). nucleotide is the key element in the formation of this DNA lesion, electron attachment might be one of the important factors that trigger the formation of abasic sites in DNA double helices. PMID:17949223

  14. Effect of cluster environment on the electron attachment to 2-nitrophenol*

    NASA Astrophysics Data System (ADS)

    Kočišek, Jaroslav; Grygoryeva, Kateryna; Lengyel, Jozef; Fárník, Michal; Fedor, Juraj

    2016-04-01

    Effect of cluster environment on the electron attachment to 2-nitrophenol (2NP) is studied in homogeneous 2NP clusters and heterogeneous clusters of 2NP, argon and water. The cluster environment significantly reduces fragmentation of 2NP after electron attachment. Parent cluster anions 2NPn- are primary reaction products in both, homogeneous and heterogeneous clusters. Non-dissociative electron attachment to homogeneous clusters proceeds at low energies <2 eV, presumably via dipole-supported states. In heterogeneous clusters, the interaction with low energy (<2 eV) electrons is shielded by the solvent. Surprisingly, the energetic threshold for the electron attachment rises with the number (n) of 2NP molecules in the cluster (2NP)n-. This rise can be either due to a strong change of the 2NP conformation induced by the cluster environment or due to the the competition with electron autodetachment after proton transfer that has been first observed by Allan in the formic acid dimer [M. Allan, Phys. Rev. Lett. 98, 123201 (2007)]. We observe the same threshold rise for complex Arm·(2NP)n- and H2O·(2NP)n- anions. This indicates that the electron attachment to 2-nitrophenol in cluster environment is more influenced by the solute - solute interaction compared to the solute - solvent interaction. Contribution to the Topical Issue "Advances in Positron and Electron Scattering", edited by Paulo Limao-Vieira, Gustavo Garcia, E. Krishnakumar, James Sullivan, Hajime Tanuma and Zoran Petrovic.Supplementary material in the form of one pdf file available from the Journal web page at http://dx.doi.org/10.1140/epjd/e2016-70074-0

  15. Electron attachment to the cytosine-centered DNA single strands: does base stacking matter?

    PubMed

    Gu, Jiande; Wang, Jing; Leszczynski, Jerzy

    2012-02-01

    Electron attachment to the trimer of nucleotide, dGpdCpdG, has been investigated by a quantum mechanical approach at a reliable level of theory. The study of the electron attached dGpdCpdG species demonstrates that cytosine contained DNA single strands have a strong tendency to capture low-energy electrons and to form electronically stable cytosine-centered radical anions. The comparative study of the model molecules pdCpdG and dGpdCp reveals that base stacking has little contribution to the adiabatic electron affinity (AEA) of cytosine in DNA single strands. Additionally, the base-base stacking does not affect the vertical detachment energy (VDE) of the cytosine-centered radicals. Intrastrand H-bonding is found to be critical in increasing the values of the AEA and VDE. However, base-base stacking is revealed to be important in enlarging the vertical electron affinity (VEA) of cytosine. The electron attachment to the cytosine moiety intensifies the intrastrand H-bonding between the neighboring G and C bases. This process disrupts the base-base stacking interaction in the radical anion of dGpdCpdG. PMID:22225006

  16. Electronic Communications Technologies and the Transition to College: Links to Parent-Child Attachment and Adjustment

    ERIC Educational Resources Information Center

    Sarigiani, Pamela A.; Trumbell, Jill M.; Camarena, Phame M.

    2013-01-01

    Electronic communications technologies (ECTs) help college students and parents remain in contact. Because recent reports have emphasized a link between ECTs, helicopter parenting, and autonomy issues, this study focused on the significance of contact patterns for attachment and student adjustment. First-semester college students (199 female, 81…

  17. Dissociative Electron Attachment to Carbon Dioxide via the 8.2 eV Feshbach resonance

    SciTech Connect

    Slaughter, Dan; Adaniya, Hidihito; Rescigno, Tom; Haxton, Dan; Orel, Ann; McCurdy, Bill; Belkacem, Ali

    2011-08-17

    Momentum imaging experiments on dissociative electron attachment (DEA) to CO{sub 2} are combined with the results of ab initio calculations to provide a detailed and consistent picture of the dissociation dynamics through the 8.2 eV resonance, which is the major channel for DEA in CO{sub 2}. The present study resolves several puzzling misconceptions about this system.

  18. Dissociative electron attachment to C{sub 2}F{sub 5} radicals

    SciTech Connect

    Haughey, Sean A.; Field, Thomas A.; Langer, Judith; Shuman, Nicholas S.; Miller, Thomas M.; Friedman, Jeffrey F.; Viggiano, A. A.

    2012-08-07

    Dissociative electron attachment to the reactive C{sub 2}F{sub 5} molecular radical has been investigated with two complimentary experimental methods; a single collision beam experiment and a new flowing afterglow Langmuir probe technique. The beam results show that F{sup -} is formed close to zero electron energy in dissociative electron attachment to C{sub 2}F{sub 5}. The afterglow measurements also show that F{sup -} is formed in collisions between electrons and C{sub 2}F{sub 5} molecules with rate constants of 3.7 Multiplication-Sign 10{sup -9} cm{sup 3} s{sup -1} to 4.7 Multiplication-Sign 10{sup -9} cm{sup 3} s{sup -1} at temperatures of 300-600 K. The rate constant increases slowly with increasing temperature, but the rise observed is smaller than the experimental uncertainty of 35%.

  19. Dissociative Electron Attachment to Thymine: Bond and Site Selectivity in Different Molecular Environments

    NASA Astrophysics Data System (ADS)

    Denifl, Stephan; Ptasińska, Sylwia; Zappa, Fabio; Mähr, Ingo; Grill, Verena; Probst, Michael; Illenberger, Eugen; Märk, Tilmann D.; Scheier, Paul

    2007-04-01

    Low energy electrons effectively decompose thymine via dissociative electron attachment inducing H loss below 3 eV and H- loss above 5 eV. Experiments with partially deuterated or methylated thymine show that the site of dehydrogenation can be precisely controlled by the incident electron energy. Such bond and site selectivity also remains in more complex environments when thymine is a moiety of thymidine (base+sugar unit) and of a thymine cluster embedded in a superfluid helium droplet. Implications for the interpretation of strand breaks in plasmid DNA induced by low energy electrons are discussed.

  20. Threshold Electron-Molecule Attachment at Sub-meV Resolution

    NASA Astrophysics Data System (ADS)

    Kortyna, A.; Darrach, M.; Chutjian, A.

    1998-05-01

    The technique of rare-gas photoionization is used to study the attachment of electrons to SF6 at near-threshold energies. Tunable ultraviolet light ( ~ 276 nm), produced using standard pulsed laser and nonlinear mixing techniques, is frequency triple in a free jet of xenon. The resulting vacuum ultraviolet radiation ( ~ 92 nm) ionizes xenon near its ^2 P_1/2 threshold. Subsequent photoelectrons, characterized by a very narrow energy distribution of δ ɛ<0.5 meV with ɛ<100 meV, interact with SF6 in a 4 π steradian scattering arrangement. The Wigner threshold law is tested at low energies. As expected, the electron attachment cross section shows an approximate ɛ-1/2 dependence for 0< ɛ C 45 meV. At ɛ ≈ 45 meV, however, a steep drop in the attachment cross section reveals the opening of a previously unobserved inelastic channel associated with one quanta of the ω6 vibrational mode of SF6 predicted to occur at ɛ = 44 meV. Future investigations into the behavior of the electron attachment cross section near-threshold are planned. This work was carried out at JPL/Caltech and supported through agreement with NASA.

  1. Importance of nonresonant scattering in low-energy dissociative electron attachment to molecular hydrogen.

    PubMed

    Rabli, Djamal; Morrison, Michael A

    2006-07-01

    A central premise of nearly all theories of dissociative electron attachment is that this process is resonance driven. Neglect of nonresonant scattering, although appropriate for electron-molecule systems with narrow (long-lived) resonances, is problematic for the e-H2 system, which has one of the broadest known resonances. Using the nonadiabatic phase-matrix method we have found that at energies from threshold to 6 eV contributions from nonresonant scattering to cross sections to dissociative attachment to in its ground vibrational and electronic state exceed 60%. Comparison of theoretical and experimental cross sections argue strongly for further efforts to resolve the considerable remaining discrepancies over this most elementary rearrangement process. PMID:16907375

  2. High resolution low-energy electron attachment to CF3I

    NASA Astrophysics Data System (ADS)

    Marienfeld, S.; Fabrikant, I. I.; Braun, M.; Ruf, M.-W.; Hotop, H.

    2006-01-01

    Using several variants of the laser photoelectron attachment method, we have measured the energy-dependent yield for I- formation resulting from dissociative electron attachment (DEA) to CF3I molecules over the energy range 0.5-500 meV. One approach involved a static target gas (TG = 300 K) and pulsed electron production/anion extraction. In another approach, a collimated target was provided by a differentially pumped, seeded supersonic beam (10% CF3I in helium carrier gas, stagnation pressure 1 bar, nozzle temperature 300 K and 600 K). At the onsets for excitation of one and two quanta for the C-I stretching mode ν3, clear downward cusps are detected. With reference to the recommended thermal DEA rate coefficient kA(Te = TG = 300 K) = 1.9 × 10-7 cm3 s-1, a new highly resolved absolute cross section for I- formation has been determined. Our experimental results are well reproduced by a cross section calculated in the framework of the resonance R-matrix theory. The input for the theory includes the known energetic and structural parameters of the neutral molecule and its anion and adopts a revised vertical attachment energy and a surface amplitude chosen to reproduce the thermal DEA rate coefficient. The theory is also applied to predict absolute cross sections for vibrational excitation of the C-I stretching mode ν3. Using our experimental and theoretical DEA cross sections we derive rate coefficients for Rydberg electron transfer (RET) and the dependence of the rate coefficients for free electron attachment of a Maxwellian electron ensemble on the mean electron energy from 0.002 to 2 eV at the constant gas temperature TG = 300 K; in both cases good agreement is observed with direct RET and swarm measurements.

  3. Early time evolution of negative ion clouds and electron density depletions produced during electron attachment chemical release experiments

    NASA Technical Reports Server (NTRS)

    Scales, W. A.; Bernhardt, P. A.; Ganguli, G.

    1994-01-01

    Two-dimensional electrostatic particle-in-cell simulations are used to study the early time evolution of electron depletions and negative ion clouds produced during electron attachment chemical releases in the ionosphere. The simulation model considers the evolution in the plane perpendicular to the magnetic field and a three-species plasma that contains electrons, positive ions, and also heavy negative ions that result as a by-product of the electron attachment reaction. The early time evolution (less than the negative ion cyclotron period) of the system shows that a negative charge surplus initially develops outside of the depletion boundary as the heavy negative ions move across the boundary. The electrons are initially restricted from moving into the depletion due to the magnetic field. An inhomogenous electric field develops across the boundary layer due to this charge separation. A highly sheared electron flow velocity develops in the depletion boundary due to E x B and Delta-N x B drifts that result from electron density gradients and this inhomogenous electric field. Structure eventually develops in the depletion boundary layer due to low-frequency electrostatic waves that have growth times shorter than the negative ion cyclotron period. It is proposed that these waves are most likely produced by the electron-ion hybrid instability that results from sufficiently large shears in the electron flow velocity.

  4. Rate coefficients for dissociative attachment and resonant electron-impact dissociation involving vibrationally excited O{sub 2} molecules

    SciTech Connect

    Laporta, V.; Celiberto, R.; Tennyson, J.

    2014-12-09

    Rate coefficients for dissociative electron attachment and electron-impact dissociation processes, involving vibrationally excited molecular oxygen, are presented. Analytical fits of the calculated numerical data, useful in the applications, are also provided.

  5. Analysis by kinetic modeling of the temperature dependence of thermal electron attachment to CF3Br.

    PubMed

    Troe, Jürgen; Miller, Thomas M; Shuman, Nicholas S; Viggiano, Albert A

    2012-07-14

    Experimental data from the literature for cross sections and rate constants for dissociative electron attachment to CF(3)Br, with separately varied electron and gas temperatures, are analyzed by a kinetic modeling approach. The analysis suggests that electronic and nuclear contributions to the rate constants can be roughly separated, the former leading to a negative temperature coefficient, the latter to a positive temperature coefficient. The nuclear factor in the rate constant is found to be of Arrhenius form with an activation energy which is close to the energy of crossing of the CF(3)Br and CF(3)Br(-) potential curves along the CBr bond. PMID:22803532

  6. Anomalously Large Chiral Sensitivity in the Dissociative Electron Attachment of 10-Iodocamphor

    NASA Astrophysics Data System (ADS)

    Dreiling, J. M.; Lewis, F. W.; Mills, J. D.; Gay, T. J.

    2016-03-01

    We have studied dissociative electron attachment (DEA) between low energy (≤0.6 eV ) longitudinally polarized electrons and gas-phase chiral targets of 3-bromocamphor (C10 H15 BrO ), 3-iodocamphor (C10 H15 IO ), and 10-iodocamphor. The DEA rate depends on the sign of the incident electron helicity for a given target handedness, and it varies with both the atomic number (Z ) and location of the heaviest atom in the molecule. While simple dynamic mechanisms can account for the asymmetry dependence on Z , they fail to explain the large asymmetry variation with the heavy atom location.

  7. Anomalously Large Chiral Sensitivity in the Dissociative Electron Attachment of 10-Iodocamphor.

    PubMed

    Dreiling, J M; Lewis, F W; Mills, J D; Gay, T J

    2016-03-01

    We have studied dissociative electron attachment (DEA) between low energy (≤0.6  eV) longitudinally polarized electrons and gas-phase chiral targets of 3-bromocamphor (C_{10}H_{15}BrO), 3-iodocamphor (C_{10}H_{15}IO), and 10-iodocamphor. The DEA rate depends on the sign of the incident electron helicity for a given target handedness, and it varies with both the atomic number (Z) and location of the heaviest atom in the molecule. While simple dynamic mechanisms can account for the asymmetry dependence on Z, they fail to explain the large asymmetry variation with the heavy atom location. PMID:26991173

  8. Increased response of the reversal electron attachment detector and modeling of ion space-charge effects

    NASA Technical Reports Server (NTRS)

    Boumsellek, S.; Chutjian, A.

    1992-01-01

    Design and sensitivity tests of a modified version of the so-called reversal electron attachment detector (READ) are presented. The new version uses a spherical cathode capable of emitting higher electron currents. As in the original READ (which used a planar emitter) electrons are focused into an electrostatic mirror which reverses their trajectories. In the reversal region electrons have essentially zero energy and attach to target molecules to form negative ions. The electron gun lens system has been modified using a field and trajectory code with space charge included. Electron trajectories have been calculated for 1-mA current focused into a reversal region of 3.5-mm diameter. The detection limit of the apparatus is approximately 25 times lower than for the original READ. Nonlinearity in the measured signal vs electron current is described by a model in which a spherical ball of ions expands outward with velocity determined by the space-charge force and the initial velocity of ion formation.

  9. Electron beam controlled covalent attachment of small organic molecules to graphene

    NASA Astrophysics Data System (ADS)

    Markevich, Alexander; Kurasch, Simon; Lehtinen, Ossi; Reimer, Oliver; Feng, Xinliang; Müllen, Klaus; Turchanin, Andrey; Khlobystov, Andrei N.; Kaiser, Ute; Besley, Elena

    2016-01-01

    The electron beam induced functionalization of graphene through the formation of covalent bonds between free radicals of polyaromatic molecules and C&z.dbd;C bonds of pristine graphene surface has been explored using first principles calculations and high-resolution transmission electron microscopy. We show that the energetically strongest attachment of the radicals occurs along the armchair direction in graphene to carbon atoms residing in different graphene sub-lattices. The radicals tend to assume vertical position on graphene substrate irrespective of direction of the bonding and the initial configuration. The ``standing up'' molecules, covalently anchored to graphene, exhibit two types of oscillatory motion - bending and twisting - caused by the presence of acoustic phonons in graphene and dispersion attraction to the substrate. The theoretically derived mechanisms are confirmed by near atomic resolution imaging of individual perchlorocoronene (C24Cl12) molecules on graphene. Our results facilitate the understanding of controlled functionalization of graphene employing electron irradiation as well as mechanisms of attachment of impurities via the processing of graphene nanoelectronic devices by electron beam lithography.The electron beam induced functionalization of graphene through the formation of covalent bonds between free radicals of polyaromatic molecules and C&z.dbd;C bonds of pristine graphene surface has been explored using first principles calculations and high-resolution transmission electron microscopy. We show that the energetically strongest attachment of the radicals occurs along the armchair direction in graphene to carbon atoms residing in different graphene sub-lattices. The radicals tend to assume vertical position on graphene substrate irrespective of direction of the bonding and the initial configuration. The ``standing up'' molecules, covalently anchored to graphene, exhibit two types of oscillatory motion - bending and twisting - caused

  10. Signatures of bond formation and bond scission dynamics in dissociative electron attachment to methane.

    PubMed

    Douguet, N; Slaughter, D S; Adaniya, H; Belkacem, A; Orel, A E; Rescigno, T N

    2015-10-14

    We present a combined experimental and theoretical investigation of the dynamics and angular dependence of dissociative electron attachment to methane. We show that a triply degenerate (T2) Feshbach resonance is responsible for the broad 10 eV dissociation peak in methane. This resonance alone is shown to correlate asymptotically to the various dissociation channels observed experimentally. The molecular-frame entrance amplitude for electron attachment is calculated for each component of the threefold degenerate resonance. By investigating the topology of the anion potential energy surfaces, we deduce the main pathways to two- and three-body breakup channels involving both bond scission and bond formation. The computed fragment angular distributions reproduce the main trends of the experimental measurements. PMID:26371546

  11. Resonance electron attachment to plant hormones and its likely connection with biochemical processes

    NASA Astrophysics Data System (ADS)

    Pshenichnyuk, Stanislav A.; Modelli, Alberto

    2014-01-01

    Gas-phase formation of temporary negative ion states via resonance attachment of low-energy (0-6 eV) electrons into vacant molecular orbitals of salicylic acid (I) and its derivatives 3-hydroxy- (II) and 4-hydroxybenzoic acid (III), 5-cloro salicylic acid (IV) and methyl salicylate (V) was investigated for the first time by electron transmission spectroscopy. The description of their empty-level structures was supported by density functional theory and Hartree-Fock calculations, using empirically calibrated linear equations to scale the calculated virtual orbital energies. Dissociative electron attachment spectroscopy (DEAS) was used to measure the fragment anion yields generated through dissociative decay channels of the parent molecular anions of compounds I-V, detected with a mass filter as a function of the incident electron energy in the 0-14 eV energy range. The most intense negative fragment produced by DEA to isomers I-III is the dehydrogenated molecular anion [M-H]-, mainly formed at incident electron energies around 1 eV. The vertical and adiabatic electron affinities were evaluated at the B3LYP/6-31+G(d) level as the anion/neutral total energy difference. The same theoretical method was also used for evaluation of the thermodynamic energy thresholds for production of the negative fragments observed in the DEA spectra. The gas-phase DEAS data can provide support for biochemical reaction mechanisms in vivo.

  12. Resonance electron attachment to plant hormones and its likely connection with biochemical processes

    SciTech Connect

    Pshenichnyuk, Stanislav A.; Modelli, Alberto

    2014-01-21

    Gas-phase formation of temporary negative ion states via resonance attachment of low-energy (0–6 eV) electrons into vacant molecular orbitals of salicylic acid (I) and its derivatives 3-hydroxy- (II) and 4-hydroxybenzoic acid (III), 5-cloro salicylic acid (IV) and methyl salicylate (V) was investigated for the first time by electron transmission spectroscopy. The description of their empty-level structures was supported by density functional theory and Hartree-Fock calculations, using empirically calibrated linear equations to scale the calculated virtual orbital energies. Dissociative electron attachment spectroscopy (DEAS) was used to measure the fragment anion yields generated through dissociative decay channels of the parent molecular anions of compounds I–V, detected with a mass filter as a function of the incident electron energy in the 0–14 eV energy range. The most intense negative fragment produced by DEA to isomers I–III is the dehydrogenated molecular anion [M–H]{sup −}, mainly formed at incident electron energies around 1 eV. The vertical and adiabatic electron affinities were evaluated at the B3LYP/6-31+G(d) level as the anion/neutral total energy difference. The same theoretical method was also used for evaluation of the thermodynamic energy thresholds for production of the negative fragments observed in the DEA spectra. The gas-phase DEAS data can provide support for biochemical reaction mechanisms in vivo.

  13. Dissociative electron attachments to ethanol and acetaldehyde: A combined experimental and simulation study

    SciTech Connect

    Wang, Xu-Dong; Xuan, Chuan-Jin; Feng, Wen-Ling; Tian, Shan Xi

    2015-02-14

    Dissociation dynamics of the temporary negative ions of ethanol and acetaldehyde formed by the low-energy electron attachments is investigated by using the anion velocity map imaging technique and ab initio molecular dynamics simulations. The momentum images of the dominant fragments O{sup −}/OH{sup −} and CH{sub 3}{sup −} are recorded, indicating the low kinetic energies of O{sup −}/OH{sup −} for ethanol while the low and high kinetic energy distributions of O{sup −} ions for acetaldehyde. The CH{sub 3}{sup −} image for acetaldehyde also shows the low kinetic energy. With help of the dynamics simulations, the fragmentation processes are qualitatively clarified. A new cascade dissociation pathway to produce the slow O{sup −} ion via the dehydrogenated intermediate, CH{sub 3}CHO{sup −} (acetaldehyde anion), is proposed for the dissociative electron attachment to ethanol. After the electron attachment to acetaldehyde molecule, the slow CH{sub 3}{sup −} is produced quickly in the two-body dissociation with the internal energy redistributions in different aspects before bond cleavages.

  14. Carbon monoxide dissociative attachment and resonant dissociation by electron-impact

    NASA Astrophysics Data System (ADS)

    Laporta, V.; Tennyson, J.; Celiberto, R.

    2016-02-01

    Low-energy dissociative electron attachment and resonant electron impact dissociation of CO molecule are considered. Ro-vibrationally resolved cross sections and rate coefficients for both the processes are calculated using an ab-initio model based on the low-lying \\text{X}{{}2}\\Pi resonance of CO-. Final results show that the cross sections increases very rapidly as a function of the ro-vibrational level; these cross sections should be useful for understanding kinetic dissociation of CO in strongly non-equilibrium plasmas.

  15. Explosion of electron bubbles attached to quantized vortices in liquid {sup 4}He

    SciTech Connect

    Pi, Marti; Mayol, Ricardo; Hernando, Alberto; Barranco, Manuel; Ancilotto, Francesco

    2007-06-28

    Electron bubbles in superfluid {sup 4}He have been recently observed in low-temperature cavitation measurements under experimental conditions where quantized vortices are also present in the liquid, and which might be attached to the bubbles. We have calculated, within density functional theory, the structure and energetics of electron bubbles pinned to linear vortices in liquid {sup 4}He at low temperature, and the pressure at which such structures become mechanically unstable. Our results are in semiquantitative agreement with the experiments. We discuss dynamical effects not included in the theoretical model used in the present calculations, and which could explain some discrepancies between our results and the experimental data.

  16. Studying dissociative electron attachment through formation of heavy-Rydberg ion-pair states

    NASA Astrophysics Data System (ADS)

    Kelley, Michael; Buathong, Sitti; Dunning, F. Barry

    2016-05-01

    Following dissociative electron transfer in collisions between Rydberg atoms and electron-attaching targets, it is possible for the resulting pair of ions to remain electrostatically bound, forming heavy-Rydberg ion-pair states. Precise measurement of the velocity distributions of such ion-pair states provides information concerning the dissociation dynamics of the excited intermediates initially created by electron transfer. Here, electric-field-induced dissociation is used to detect the product ion pairs and observe their velocity distributions. These distributions are analyzed with the aid of a Monte Carlo collision code that models the electron transfer. Measurements with a number of different target species show that through this analysis, dissociation energetics, the branching ratios into different dissociation products, and the lifetimes of the excited intermediates can be examined. Research supported by the Robert A. Welch Foundation.

  17. Theory of radiative electron attachment to molecules: Benchmark study of CN-

    NASA Astrophysics Data System (ADS)

    Douguet, Nicolas; Fonseca dos Santos, Samantha; Raoult, Maurice; Dulieu, Olivier; Orel, Ann E.; Kokoouline, Viatcheslav

    2013-11-01

    We have developed an approach based on first principles to study the process of radiative electron attachment (REA) to linear molecules of astrophysical interest in collisions between the molecules and electrons at energies below 1 eV. The approach is based on accurate ab initio calculations of electronic bound and continuum states of the negative ion. The electronic continuum states are obtained with the complex-Kohn variational method. The benchmark calculation for the REA to the simplest negative ion CN-, which was recently observed in the interstellar medium, has produced a relatively low rate coefficient α(T)=7.3×10-16 cm3/s at T=30 K. Moreover, our results are shown to agree well with microscopic reversibility applied on a recent photodetachment experiment on CN-. Finally, the study confirms a previous assessment that the CN- ion is unlikely be formed by REA in the interstellar medium.

  18. Radiative electron attachment to molecules of astrophysical interest. Benchmark study of CN^-.

    NASA Astrophysics Data System (ADS)

    Kokoouline, Viatcheslav; Douguet, Nicolas; Dulieu, Olivier; Raoult, Maurice; Orel, Ann E.

    2012-06-01

    We develop a first-principles approach to study the process of radiative electron attachment (REA) to linear molecules of astrophysical interest Mol +e^- ->Mol^- + φ. (Mol^- = CnH^-, CnN^-). The approach is based on accurate ab initio calculations of electronic bound and continuum states of the negative ion. The electronic continuum states are obtained with the complex-Kohn variational method. A preliminary calculation for the formation of the simplest observed ion, CN^-, by REA gave a low rate coefficient. We will present also a preliminary result for the C4H^- formation by REA. For this molecule, the REA rate coefficient is expected to be somewhat larger due to the Renner-Teller non-adiabatic coupling that should enhance electron capture. The goal of this study is to answer the question if negative molecular ions CnH^- and CnN^- recently observed in the interstellar space could indeed be formed by REA as previously suggested.

  19. Simulation of high-speed (orbital) releases of electron attachment materials in the ionosphere

    NASA Technical Reports Server (NTRS)

    Scales, W. A.; Bernhardt, P. A.

    1991-01-01

    The dynamics of ionospheric plasma irregularities produced by the release of electron attachment materials at orbital velocities across the geomagnetic field is studied. A two-dimensional electrostatic fluid model which includes electron attachment and mutual neutralization chemistry, self-consistent electric fields, and three-species transport is developed. Numerical simulations are performed to study the behavior at early and at late times after the release. At early times, of the order of or less than the attachment material neutral collision time, the negative ion cloud produced by the release may structure owing to the shear in the E x B velocity within the cloud. At high altitudes the cloud may bifurcate and form vortices on the back. At lower altitudes where ion-neutral collisional effects dominate, this structuring is suppressed. At late times, after a plasma depletion has formed due to neutralization chemistry, the cloud structures by the E x B interchange instability. Depending on the release altitude, the depletion structures by the collisional or inertial limit of this instability.

  20. Oxygen Attachment on Alkanethiolate SAMs Induced by Low-Energy Electron Irradiation

    PubMed Central

    Massey, Sylvain; Bass, Andrew D.; Steffenhagen, Marie; Sanche, Léon

    2013-01-01

    Reactions of 18O2 with self-assembled monolayer (SAM) films of 1-dodecanethiol, 1-octadecanethiol, 1-butanethiol, and benzyl mercaptan chemisorbed on gold, were studied by the electron stimulated desorption (ESD) of anionic fragments over the incident electron energy range 2–20 eV. Dosing the SAMs with 18O2 at 50 K, results in the ESD of 18O− and 18OH−. Electron irradiation of samples prior to 18O2 deposition demonstrates that intensity of subsequent 18O− and 18OH− desorption signals increase with electron fluence and that absent electron pre-irradiation, no 18O− and 18OH− ESD signals are observed, since oxygen is unable to bind to the SAMs. A minimum incident electron energy of 6–7 eV is required to initiate the binding of 18O2 to the SAMs. O2 binding is proposed to proceed by the formation of CHx−1• radicals via resonant dissociative electron attachment and non-resonant C–H dissociation processes. The weaker signals of 18O− and 18OH− from short-chain SAMs are related to the latter’s resistance to electron induced damage, due to the charge-image dipole quenching and electron delocalization. Comparison between the present results and those for DNA oligonucleotides self-assembled on Au [Mirsaleh-Kohan, N. et al. J. Chem. Phys. 2012, 136, 235104] indicates that the oxygen binding mechanism is common to both systems. PMID:23537075

  1. Observation of the dynamics leading to a conical intersection in dissociative electron attachment to water

    SciTech Connect

    Haxton, D.; Adaniya, H.; Slaughter, D. S.; Rudek, B.; Osipov, T.; Weber, T.; Rescigno, T. N.; McCurdy, C. W.; Belkacem, A.

    2011-08-11

    Following prior work on the lower-energy resonances, we apply techniques of momentum imaging and ab initio scattering calculations to the process of dissociative electron attachment to water via the highest-energy {sup 2}B{sub 2} resonance. We focus on the H{sup -} anion fragment, which is produced via dynamics passing through and avoiding the conical intersection with the lower A{sub 1} state, leading to OH ({sup 2}{Pi} ) and OH ({sup 2}{Sigma} ), respectively. The momentum imaging technique, when combined with theoretical calculations on the attachment amplitude and dissociation dynamics, demonstrates that the angular distributions provide a signature of the location of the conical intersection in the space of nuclear configurations.

  2. Observation of the dynamics leading to a conical intersection in dissociative electron attachment to water

    SciTech Connect

    Haxton, Dan; Adaniya, Hidihito; Slaughter, Dan; Rudek, B.; Osipov, Timur; Weber, Thorsten; Rescigno, Tom; McCurdy, Bill; Belkacem, Ali

    2011-06-08

    Following prior work on the lower-energy resonances, we apply techniques of momentum imaging and ab initio scattering calculations to the process of dissociative electron attachment to water via the highest-energy {sup 2}B{sub 2} resonance. We focus on the H{sup -} anion fragment, which is produced via dynamics passing through and avoiding the conical intersection with the lower A{sub 1} state, leading to OH ((sup 2}{Pi}#5;) and OH ({sup 2}{Sigma}#6;), respectively. The momentum imaging technique, when combined with theoretical calculations on the attachment amplitude and dissociation dynamics, demonstrates that the angular distributions provide a signature of the location of the conical intersection in the space of nuclear con#12;gurations.

  3. Electron beam controlled covalent attachment of small organic molecules to graphene.

    PubMed

    Markevich, Alexander; Kurasch, Simon; Lehtinen, Ossi; Reimer, Oliver; Feng, Xinliang; Müllen, Klaus; Turchanin, Andrey; Khlobystov, Andrei N; Kaiser, Ute; Besley, Elena

    2016-02-01

    The electron beam induced functionalization of graphene through the formation of covalent bonds between free radicals of polyaromatic molecules and C=C bonds of pristine graphene surface has been explored using first principles calculations and high-resolution transmission electron microscopy. We show that the energetically strongest attachment of the radicals occurs along the armchair direction in graphene to carbon atoms residing in different graphene sub-lattices. The radicals tend to assume vertical position on graphene substrate irrespective of direction of the bonding and the initial configuration. The "standing up" molecules, covalently anchored to graphene, exhibit two types of oscillatory motion--bending and twisting--caused by the presence of acoustic phonons in graphene and dispersion attraction to the substrate. The theoretically derived mechanisms are confirmed by near atomic resolution imaging of individual perchlorocoronene (C24Cl12) molecules on graphene. Our results facilitate the understanding of controlled functionalization of graphene employing electron irradiation as well as mechanisms of attachment of impurities via the processing of graphene nanoelectronic devices by electron beam lithography. PMID:26757842

  4. Low energy electron attachment to cyanamide (NH{sub 2}CN)

    SciTech Connect

    Tanzer, Katrin; Denifl, Stephan E-mail: Stephan.Denifl@uibk.ac.at; Pelc, Andrzej E-mail: Stephan.Denifl@uibk.ac.at; Huber, Stefan E.; Czupyt, Z.

    2015-01-21

    Cyanamide (NH{sub 2}CN) is a molecule relevant for interstellar chemistry and the chemical evolution of life. In the present investigation, dissociative electron attachment to NH{sub 2}CN has been studied in a crossed electron–molecular beams experiment in the electron energy range from about 0 eV to 14 eV. The following anionic species were detected: NHCN{sup −}, NCN{sup −}, CN{sup −}, NH{sub 2}{sup −}, NH{sup −}, and CH{sub 2}{sup −}. The anion formation proceeds within two broad electron energy regions, one between about 0.5 and 4.5 eV and a second between 4.5 and 12 eV. A discussion of possible reaction channels for all measured negative ions is provided. The experimental results are compared with calculations of the thermochemical thresholds of the anions observed. For the dehydrogenated parent anion, we explain the deviation between the experimental appearance energy of the anion with the calculated corresponding reaction threshold by electron attachment to the isomeric form of NH{sub 2}CN—carbodiimide.

  5. Radiative electron attachment to molecules of astrophysical interest. Benchmark study of CN-

    NASA Astrophysics Data System (ADS)

    Kokoouline, Viatcheslav; Douguet, Nicolas; Fonseca Dos Santos, Samantha; Dulieu, Olivier; Raoult, Maurice; Orel, Ann; ? Collaboration

    2013-03-01

    We have developed a first-principles approach to study the process of radiative electron attachment (REA) to linear molecules of astrophysical interest Mol +e- --> Mol- + ℏω . (Mol- = CnH-, CnN-). The approach is based on accurate ab initio calculations of electronic bound and continuum states of the negative ion. The electronic continuum states are obtained with the complex-Kohn variational method. The benchmark calculation for the formation of the simplest observed ion, CN-, by REA has produced a low rate coefficient, 5 ×10-17 cm3 / s at 30 K. We will present also a preliminary result for the C4H- formation by REA. For this molecule, the REA rate coefficient is expected is larger by about a factor of 10 due to a larger transition dipole moment. This study suggests that the negative molecular ions, recently observed in the interstellar medium, can hardly be formed by the process of radiative electron attachment. This work is supported by the DOE Office of Basic Energy Science and the National Science Foundation, Grant No's PHY-08-55092 and PHY-08-55622.

  6. The dependence of low-energy electron attachment to CF3Br on electron and vibrational energy.

    PubMed

    Marienfeld, S; Sunagawa, T; Fabrikant, I I; Braun, M; Ruf, M-W; Hotop, H

    2006-04-21

    In a joint experimental and theoretical effort, we have studied dissociative electron attachment (DEA) to the CF3Br molecule at electron energies below 2 eV. Using two variants of the laser photoelectron attachment method with a thermal gas target (T(G) = 300 K), we measured the energy dependent yield for Br- formation over the range E = 3-1200 meV with resolutions of about 3 meV (E < 200 meV) and 35 meV. At the onsets for excitation of one and two quanta for the C-Br stretching mode nu3, downward cusps are detected. With reference to the recommended thermal (300 K) attachment rate coefficient k(A)(CF3Br) = 1.4 x 10(-8) cm3 s(-1), absolute cross sections have been determined for Br- formation. In addition, we studied Br- and (CF3Br)Br- formations with a seeded supersonic target beam (10% CF3Br in helium carrier gas, with a stagnation pressure of 1-4 bars and nozzle temperatures of 300 and 600 K) and found prominent structure in the anion yields due to cluster formation. Using the microwave pulse radiolysis swarm technique, allowing for controlled variation of the electron temperature by microwave heating, we studied the dependence of the absolute DEA rate coefficient on the mean electron energy E over the range of 0.04-2 eV at gas temperatures T(G) ranging from 173 to 600 K. For comparison with the experimental results, semiempirical resonance R-matrix calculations have been carried out. The input for the theory includes the known energetic and structural parameters of the neutral molecule and its anion; the parameters of the resonant anion curves are chosen with reference to the known thermal rate coefficient for the DEA process. For the gas temperature T(G) = 300 K, good overall agreement of the theoretical DEA cross section with the experimental results is observed; moreover, rate coefficients for Br- formation due to Rydberg electron transfer, calculated with both the experimental and the theoretical DEA cross sections, are found to agree with the previously

  7. Insensitivity of the pressure dependences of characteristic energy scales in Ce1–xRxCoIn₅ (R=Yb,Y,Gd) to the electronic configuration of the rare-earth ion

    DOE PAGESBeta

    White, B. D.; Hamlin, J. J.; Huang, K.; Shu, L.; Lum, I. K.; Baumbach, R. E.; Janoschek, M.; Maple, M. B.

    2012-09-11

    Cooperative Ce and Yb valence fluctuations have recently been proposed as the mechanism responsible for stabilizing correlated electron phenomena in Ce₁₋xYbxCoIn₅ over an unexpectedly large range of concentrations. In order to better understand the origins and character of this stability, we have measured the effect of applied pressure on relevant energy scales such as the superconducting critical (Tc) and Kondo-lattice coherence (T*) temperatures of Ce₁₋xRxCoIn₅ with R=Yb, Y, and Gd. Electrical resistivity measurements were performed under applied pressure on samples doped with intermediate-valent Yb and stable-valent Gd and Y, and the responses of Tc and T* to increased pressure inmore » these systems are compared. The character of Tc(P) and T*(P) in Ce₁₋xRxCoIn₅ depends only on their respective ambient-pressure values Tc(0) and T*(0), independent of the electronic configuration of R or concentration x. The consequences of this result are discussed within the context of possible cooperative valence fluctuations in Ce₁₋xYbxCoIn₅.« less

  8. Insensitivity of the pressure dependences of characteristic energy scales in Ce1–xRxCoIn₅ (R=Yb,Y,Gd) to the electronic configuration of the rare-earth ion

    SciTech Connect

    White, B. D.; Hamlin, J. J.; Huang, K.; Shu, L.; Lum, I. K.; Baumbach, R. E.; Janoschek, M.; Maple, M. B.

    2012-09-11

    Cooperative Ce and Yb valence fluctuations have recently been proposed as the mechanism responsible for stabilizing correlated electron phenomena in Ce₁₋xYbxCoIn₅ over an unexpectedly large range of concentrations. In order to better understand the origins and character of this stability, we have measured the effect of applied pressure on relevant energy scales such as the superconducting critical (Tc) and Kondo-lattice coherence (T*) temperatures of Ce₁₋xRxCoIn₅ with R=Yb, Y, and Gd. Electrical resistivity measurements were performed under applied pressure on samples doped with intermediate-valent Yb and stable-valent Gd and Y, and the responses of Tc and T* to increased pressure in these systems are compared. The character of Tc(P) and T*(P) in Ce₁₋xRxCoIn₅ depends only on their respective ambient-pressure values Tc(0) and T*(0), independent of the electronic configuration of R or concentration x. The consequences of this result are discussed within the context of possible cooperative valence fluctuations in Ce₁₋xYbxCoIn₅.

  9. Electron attachment to Ni(PF{sub 3}){sub 4} and Pt(PF{sub 3}){sub 4}

    SciTech Connect

    Friedman, Jeffrey F.; Miller, Thomas M.; Friedman-Schaffer, Jessica K.; Rekha, G. K.; Stevens, Amy E.; Viggiano, A. A

    2008-03-14

    An experimental study has been made of thermal electron attachment to the transition-metal trifluorophosphine complexes Ni(PF{sub 3}){sub 4} and Pt(PF{sub 3}){sub 4} using a flowing-afterglow Langmuir-probe apparatus. Both complexes are efficient at electron attachment, although the rate constants are somewhat less than collisional. The rate constant for electron attachment to Ni(PF{sub 3}){sub 4} is 1.9x10{sup -7} cm{sup 3} s{sup -1} at room temperature, about a factor of 2 less than collisional. The activation energy is 39{+-}5 meV for the attachment reaction. The rate constant for electron attachment to Pt(PF{sub 3}){sub 4} is 5.4x10{sup -8} cm{sup 3} s{sup -1} at room temperature, and the activation energy is 84{+-}8 meV. For both complexes, a PF{sub 3} ligand is lost on electron attachment, and only the M(PF{sub 3}){sub 3}{sup -} ion is observed in the negative-ion mass spectrum. Density functional calculations were carried out on Ni(PF{sub 3}){sub 4} and various fragments in order to describe the thermochemistry of the attachment reaction.

  10. Formation and Decay of the Dehydrogenated Parent Anion upon Electron Attachment to Dialanine

    PubMed Central

    Gschliesser, David; Vizcaino, Violaine; Probst, Michael; Scheier, Paul; Denifl, Stephan

    2012-01-01

    Abstract The dehydrogenated parent anion [M−H]− is one of the most dominant anions formed in dissociative electron attachment to various small biomolecules like nucleobases and single amino acids. In the present study, we investigate the [M−H]− channel for the dipeptide dialanine by utilizing an electron monochromator and a two-sector-field mass spectrometer. At electron energies below 2 eV, the measured high-resolution ion-efficiency curve has a different shape to that for the single amino acid alanine, which is explained by the altered threshold energies for formation of [M−H]− determined in quantum chemical calculations. Moreover, the structure of the formed [M−H]− anion is further studied by investigating the unimolecular and collision-induced decay of this anion. Trajectory calculations have been carried out to aid the interpretation of the experimentally observed fragmentation patterns. PMID:22374822

  11. Absolute cross sections for dissociative electron attachment to HCN and DCN

    SciTech Connect

    May, O.; Kubala, D.; Allan, M.

    2010-07-15

    Absolute partial cross sections for the formation of CN{sup -} in dissociative electron attachment to HCN and DCN have been measured using a time-of-flight ion spectrometer combined with a trochoidal electron monochromator to be 940pm{sup 2} for CN{sup -}/HCN and 340pm{sup 2} for CN{sup -}/DCN at peaks of the bands due to the {sup 2{Pi}}-shape resonance. The dissociative electron attachment bands were then recorded under higher resolution, 60 meV, with a trochoidal monochromator plus quadrupole mass filter combination and found to have a nearly vertical onset at the threshold energy and to peak at 1.85 eV. Broad structure was observed on the bands, assigned to formation of vibrationally excited CN{sup -}, from which the branching ratios could be determined to be 1,0.49, and 0.22 for the formation of CN{sup -} in the v=0,1, and 2 states, respectively. The results are compared to the recent multidimensional ab initio calculations of Chourou and Orel [Phys. Rev. A 80, 032709 (2009)].

  12. Theoretical study of radiative electron attachment to CN, C2H, and C4H radicals.

    PubMed

    Douguet, Nicolas; Fonseca dos Santos, S; Raoult, Maurice; Dulieu, Olivier; Orel, Ann E; Kokoouline, Viatcheslav

    2015-06-21

    A first-principle theoretical approach to study the process of radiative electron attachment is developed and applied to the negative molecular ions CN(-), C4H(-), and C2H(-). Among these anions, the first two have already been observed in the interstellar space. Cross sections and rate coefficients for formation of these ions by direct radiative electron attachment to the corresponding neutral radicals are calculated. For the CN molecule, we also considered the indirect pathway, in which the electron is initially captured through non-Born-Oppenheimer coupling into a vibrationally resonant excited state of the anion, which then stabilizes by radiative decay. We have shown that the contribution of the indirect pathway to the formation of CN(-) is negligible in comparison to the direct mechanism. The obtained rate coefficients for the direct mechanism at 30 K are 7 × 10(-16) cm(3)/s for CN(-), 7 × 10(-17) cm(3)/s for C2H(-), and 2 × 10(-16) cm(3)/s for C4H(-). These rates weakly depend on temperature between 10 K and 100 K. The validity of our calculations is verified by comparing the present theoretical results with data from recent photodetachment experiments. PMID:26093561

  13. Ab initio molecular dynamics simulation study of dissociative electron attachment to dialanine conformers.

    PubMed

    Feng, Wen-Ling; Tian, Shan Xi

    2015-03-12

    Dissociative electron attachment (DEA) processes of six low-lying conformers (1-6) of dialanine in the gas phase are investigated by using ab initio molecular dynamics simulations. The incoming electron is captured and primarily occupies the virtual molecular orbital π*, which is followed by the different dissociation processes. The electron attachments to conformers 1 and 2 having the stronger N-H···N and O-H···O intramolecular hydrogen bonds do not lead to fragmentations, but two different backbone bonds are broken in the DEAs to conformers 3 (or 4) and 6, respectively. It is interesting that the hydrogen abstraction of -NH from the terminal methyl group -CH3 is found in the roaming dissociation of the temporary anion of conformer 3. The present simulations enable us to have more insights into the peptide backbone bond breaks in the DEA process and demonstrate a promising way toward understanding of the radiation damages of complicated biological system. PMID:25679256

  14. Mechanisms for O/sup -/ electron stimulated desorption via dissociative attachment in condensed CO

    SciTech Connect

    Azria, R.; Parenteau, L.; Sanche, L.

    1988-04-15

    The formation of O/sup -/ ions via dissociative attachment (DA) in electron stimulated desorption from condensed CO is reported. The /sup 2/Pi states of CO/sup -/ previously observed in the gas phase and CO/sup -/ states with the forbidden symmetry ..sigma../sup -/ are involved below and above 13 eV, respectively, in the DA processes. Measurements of the kinetic energy of O/sup -/ ions indicate that they suffer post dissociation interactions with the neighboring CO molecules before leaving the solid.

  15. Dissociative attachment in electron scattering from condensed O/sub 2/ and CO

    SciTech Connect

    Sanche, L.

    1984-10-22

    The formation of O/sup -/ and C/sup -/ ions via dissociative attachment in electron scattering from O/sub 2/ and CO condensed on a polycrystalline platinum surface is reported. Below 15-eV impact energy, O/sup -/ from O/sub 2/ arises essentially from the repulsive /sup 2/Pi/sub u/ state of O/sub 2//sup -/, whereas in CO, C/sup -/ and O/sup -/ appear to be emitted from higher-energy repulsive states of CO/sup -/ with yields much different from those found for the isolated molecule.

  16. Negative-ion formation in the explosives RDX, PETN, and TNT by using the reversal electron attachment detection technique

    NASA Technical Reports Server (NTRS)

    Boumsellek, S.; Alajajian, S. H.; Chutjian, A.

    1992-01-01

    First results of a beam-beam, single-collision study of negative-ion mass spectra produced by attachment of zero-energy electrons to the molecules of the explosives RDX, PETN, and TNT are presented. The technique used is reversal electron attachment detection (READ) wherein the zero-energy electrons are produced by focusing an intense electron beam into a shaped electrostatic field which reverses the trajectory of electrons. The target beam is introduced at the reversal point, and attachment occurs because the electrons have essentially zero longitudinal and radial velocity. The READ technique is used to obtain the 'signature' of molecular ion formation and/or fragmentation for each explosive. Present data are compared with results from atmospheric-pressure ionization and negative-ion chemical ionization methods.

  17. Metabolic Electron Attachment as a Primary Mechanism For Toxicity Potentials of Halocarbons.

    PubMed

    Balasubramanian, Krishnan; Basak, Subhash C

    2016-01-01

    We have carried out systematic large-basis set quantum chemical computations at Møller- Plesset second-order perturbation (MP2) and couple cluster singles + doubles CCSD and CCSD(T)with triples correction levels of theories on a set of 55 halogenated carbons in the Crebelli toxicological dataset. We have computed a number of electronic properties at optimized geometries such as vertical electron affinities, HOMO-LUMO gaps, dipole moments, etc. We have provided insights into the mechanism of toxicity through electron attachment in metabolic pathways by binding to an electron donating enzyme in hepatocytes. The electron transfer from the enzyme to the halocarbon is accompanied by bond elongation resulting in autodetachment as evidenced from potential energy surfaces of the anion and neutral molecule. The autodetachment process leads to production of highly reactive free radicals, which cause tissue damage, and prolonged exposure can result in hepatocellular carcinoma depending on the hydrogen extraction propensity of the free radical and vertical electron affinity of the neutral halocarbon. PMID:26787161

  18. Electron attachment in F2 - Conclusive demonstration of nonresonant, s-wave coupling in the limit of zero electron energy

    NASA Technical Reports Server (NTRS)

    Chutjian, A.; Alajajian, S. H.

    1987-01-01

    Dissociative electron attachment to F2 has been observed in the energy range 0-140 meV, at a resolution of 6 meV (full width at half maximum). Results show conclusively a sharp, resolution-limited threshold behavior consistent with an s-wave cross section varying as sq rt of epsilon. Two accurate theoretical calculations predict only p-wave behavior varying as the sq rt of epsilon. Several nonadiabatic coupling effects leading to s-wave behavior are outlined.

  19. Potential energy curves via double electron-attachment calculations: Dissociation of alkali metal dimers

    NASA Astrophysics Data System (ADS)

    Musiał, Monika; Kowalska-Szojda, Katarzyna; Lyakh, Dmitry I.; Bartlett, Rodney J.

    2013-05-01

    The recently developed method [M. Musiał, J. Chem. Phys. 136, 134111 (2012), 10.1063/1.3700438] to study double electron attached states has been applied to the description of the ground and excited state potential energy curves of the alkali metal dimers. The method is based on the multireference coupled cluster scheme formulated within the Fock space formalism for the (2,0) sector. Due to the use of the efficient intermediate Hamiltonian formulation, the approach is free from the intruder states problem. The description of the neutral alkali metal dimers is accomplished via attaching two electrons to the corresponding doubly ionized system. This way is particularly advantageous when a closed shell molecule dissociates into open shell subunits while its doubly positive cation generates the closed shell fragments. In the current work, we generate the potential energy curves for the ground and multiple excited states of the Li2 and Na2 molecules. In all cases the potential energy curves are smooth for the entire range of interatomic distances (from the equilibrium point to the dissociation limit). Based on the calculated potential energy curves, we are able to compute spectroscopic parameters of the systems studied.

  20. Ab initio calculations of dissociative attachment and dissociative recombination of electrons and polyatomic species

    NASA Astrophysics Data System (ADS)

    Haxton, Daniel

    2009-05-01

    Interactions of free electrons with neutral and positively charged molecular species play a role in various physical systems. In interstellar space, reactions such as dissociative recombination determine the balance of various charged and neutral species. In a laboratory equipped with an apparatus like a COLTRIMS device, the dissociative attachment process can be used as a microscope to study polyatomic molecular dynamics. We discuss the theoretical and numerical methods used to calculate dissociative attachment and dissociative recombination of electrons with larger molecules from first principles. Studies using these methods are complimentary to other methods that yield more approximate reaction rates at greatly lesser numerical cost; they may yield precise information about the dissociation dynamics, product distribution, and differential cross section that approximate methods cannot. We discuss calculations performed to date on the target species H2O, NO2, and LiH2^+. We discuss the scaling of our numerical methods with the number of atoms, and the prospects of applying them to tetra-atomics.

  1. Covalent attachment of FeFe hydrogenases to carbon electrodes for direct electron transfer.

    PubMed

    Baffert, Carole; Sybirna, Kateryna; Ezanno, Pierre; Lautier, Thomas; Hajj, Viviane; Meynial-Salles, Isabelle; Soucaille, Philippe; Bottin, Hervé; Léger, Christophe

    2012-09-18

    Direct electron transfer between enzymes and electrodes is now commonly achieved, but obtaining protein films that are very stable may be challenging. This is particularly crucial in the case of hydrogenases, the enzymes that catalyze the biological conversion between dihydrogen and protons, because the instability of the hydrogenase films may prevent the use of these enzymes as electrocatalysts of H(2) oxidation and production in biofuel cells and photoelectrochemical cells. Here we show that two different FeFe hydrogenases (from Chamydomonas reinhardtii and Clostridium acetobutylicum) can be covalently attached to functionalized pyrolytic graphite electrodes using peptidic coupling. In both cases, a surface patch of lysine residues makes it possible to favor an orientation that is efficient for fast, direct electron transfer. High hydrogen-oxidation current densities are maintained for up to one week, the only limitation being the intrinsic stability of the enzyme. We also show that covalent attachment has no effect on the catalytic properties of the enzyme, which means that this strategy can also used be for electrochemical studies of the catalytic mechanism. PMID:22891965

  2. Direct experimental observation of weakly-bound character of the attached electron in europium anion

    PubMed Central

    Cheng, Shi-Bo; Castleman, A. W.

    2015-01-01

    Direct experimental determination of precise electron affinities (EAs) of lanthanides is a longstanding challenge to experimentalists. Considerable debate exists in previous experiment and theory, hindering the complete understanding about the properties of the atomic anions. Herein, we report the first precise photoelectron imaging spectroscopy of europium (Eu), with the aim of eliminating prior contradictions. The measured EA (0.116 ± 0.013 eV) of Eu is in excellent agreement with recently reported theoretical predictions, providing direct spectroscopic evidence that the additional electron is weakly attached. Additionally, a new experimental strategy is proposed that can significantly increase the yield of the lanthanide anions, opening up the best opportunity to complete the periodic table of the atomic anions. The present findings not only serve to resolve previous discrepancy but also will help in improving the depth and accuracy of our understanding about the fundamental properties of the atomic anions. PMID:26198741

  3. Direct experimental observation of weakly-bound character of the attached electron in europium anion.

    PubMed

    Cheng, Shi-Bo; Castleman, A W

    2015-01-01

    Direct experimental determination of precise electron affinities (EAs) of lanthanides is a longstanding challenge to experimentalists. Considerable debate exists in previous experiment and theory, hindering the complete understanding about the properties of the atomic anions. Herein, we report the first precise photoelectron imaging spectroscopy of europium (Eu), with the aim of eliminating prior contradictions. The measured EA (0.116 ± 0.013 eV) of Eu is in excellent agreement with recently reported theoretical predictions, providing direct spectroscopic evidence that the additional electron is weakly attached. Additionally, a new experimental strategy is proposed that can significantly increase the yield of the lanthanide anions, opening up the best opportunity to complete the periodic table of the atomic anions. The present findings not only serve to resolve previous discrepancy but also will help in improving the depth and accuracy of our understanding about the fundamental properties of the atomic anions. PMID:26198741

  4. Dissociative attachment in electron-stimulated desorption from condensed NO and N/sub 2/O

    SciTech Connect

    Sanche, L.; Parenteau, L.

    1986-05-01

    We have measured the intensity of O/sup -/ ions produced by low-energy electrons (1--20 eV) impinging on NO and N/sub 2/O molecules condensed on a polycrystalline platinum surface held at 17 and 40 K. In condensed NO (i.e., in the dimerized form N/sub 2/O/sub 2/), the energy dependence of the O/sup -/ yield exhibits four broad peaks within the range 5--20 eV whereas in condensed N/sub 2/O two peaks are observed at 9.4 and 16.4 eV. The linearity of O/sup -/ production near the peak energies with coverage indicates the presence of a first-order mechanism which we ascribe to the decay of transient anion states (i.e., electron resonances) into the dissociative attachment channel.

  5. Dissociative electron attachment reactions of transition metal carbonyls and their apparent influence on the thermalization of electrons by CO2

    NASA Astrophysics Data System (ADS)

    George, Patricia M.; Beauchamp, J. L.

    1982-03-01

    Dissociative electron attachment rates are measured for the transition metal carbonyls V(CO)6, Cr(CO)6, Fe(CO)5, Ni(CO)4, Mo(CO)6, and W(CO)6. Rates are measured as a function of the pressure of CO2 added to relax epithermal electrons. Derived thermal rate constants for the formation of M(CO)-n-1 from M(CO)n are 0.6, 3.0, 2.0, 2.0, 1.3, and 1.2×10-7 cm3 molecule-1 s-1, respectively. The differences in these rate constants may be attributed to the different stabilities of the molecular anion with regard to dissociation versus autodetachment. The measured rate of thermalization of electrons by CO2 varies with the metal carbonyl used and depends on the variation of the dissociative electron capture cross section with electron energy. Each system is thus tightly coupled in that the electron energy distribution is determined not only by collisional processes involving CO2 but varies as well with the energy dependent depletion of the distribution by reactant species.

  6. Explicitly correlated equation-of-motion coupled-cluster methods for excited and electron-attached states.

    PubMed

    Bokhan, Denis; Ten-No, Seiichiro

    2010-11-28

    Based on the linearly approximated F12 coupled cluster singles and doubles [CCSD(F12)] model, equation-of-motion [EOM-CCSD(F12)] methods for electron affinities (EAs) and excitation energies (EEs) have been formulated and implemented. Extended electron-attachment and excitation operators are introduced for balanced descriptions of both neutral and electron-attached (or excited) states. In our implementation the cusp conditions are used for the definition of extended electron-attachment (excitation) operators. It is shown that EA-EOM-CCSD(F12) provides vertical electron affinities accurate to 0.1 eV compared to those in the complete basis set limit. Numerical tests conducted on a selection of small molecules have also shown notable improvement in Rydberg excitation energies compared to valence ones by the use of correlation factors. PMID:21133437

  7. Dissociative electron attachment and charging of SF6 adsorbed on rare-gas films

    NASA Astrophysics Data System (ADS)

    Weik, Fritz; Illenberger, Eugen

    1998-10-01

    Electron stimulated desorption (ESD) of fragment ions in the energy range between 0 and 18 eV from SF6 adsorbed on rare-gas films (Kr, Xe) is reported. The ESD results are compared with previous experiments on dissociative electron attachment (DA) to gas-phase SF6. At energies characteristic for the respective rare-gas substrate strong resonant enhancements in the ESD yield of F- are observed. This enhancement is explained by the appearance of an "electron-exciton complex" in the rare-gas film (the analogue to the anionic Feshbach resonances in single atoms) which couples to the first dipole allowed excitation of the SF6 molecule. After electron and energy transfer, the highly excited SF6*- ion dissociates at the surface resulting in the desorption of F- fragments. At low electron energies (in the range from 0 to 0.6 eV) charging of the rare-gas film covered with SF6 is observed. From these experiments a charging cross section of 2.1(±1.8)×10-15 cm2 is derived.

  8. Formation of Negative Ions upon Dissociative Electron Attachment to the Astrochemically Relevant Molecule Aminoacetonitrile.

    PubMed

    Pelc, Andrzej; Huber, Stefan E; Matias, Carolina; Czupyt, Zbigniew; Denifl, Stephan

    2016-02-18

    Aminoacetonitrile (NH2CH2CN, AAN) is a molecule relevant for interstellar chemistry and the chemical evolution of life. It is a very important molecule in the Strecker diagram explaining the formation of amino acids. In the present investigation, dissociative electron attachment to NH2CN was studied in a crossed electron-molecular beams experiment in the electron energy range from about 0 to 17 eV. In this electron energy range, the following six anionic species were detected: C2H3N2(-), C2H2N2(-), C2H2N(-), C2HN(-), CN(-), and NH2(-). Possible reaction channels for all the measured negative ions are discussed, and the experimental results are compared with calculated thermochemical thresholds of the observed anions. Similar to other nitrile and aminonitrile compounds, the main anions detected were the negatively charged nitrile group, the dehydrogenated parent molecule, and the amino group. No parent anion was observed. Low anion yields were observed indicating that AAN is less prone to electron capture. Therefore, AAN can be considered to exhibit a relatively long lifetime under typical conditions in outer space. PMID:26810336

  9. Mitigation of electron attachment to oxygen in high pressure air plasmas by vibrational excitation

    NASA Astrophysics Data System (ADS)

    Frederickson, K.; Lee, W.; Palm, P.; Adamovich, I. V.; Rich, J. W.; Lempert, W. R.

    2007-05-01

    A series of time resolved microwave attenuation measurements are performed of the electron number density of an electron beam generated, CO laser excited nonequilibrium O2/N2 plasma. Resonant absorption of infrared radiation from the CO laser produces the nonequilibrium state, in which the heavy species vibrational modes are disproportionately excited, compared to the rotational and translational modes (Tvib≈2000-3000K vs TR /T≈300K). It is shown that this results in an increase in the plasma free electron lifetime by two orders of magnitude compared to the unexcited cold gas, an effect which is ascribed to complete mitigation of rapid three-body electron attachment to molecular oxygen. A series of heavy species filtered pure rotational Raman scattering measurements are also presented, which exhibit minimal temperature change (+50K), indicating that the observed lifetime increase cannot be due to heavy-species thermal effects. Finally, computational modeling results infer an increase in the rate of O2- detachment by four to five orders of magnitude, compared to the equilibrium value.

  10. SF-6 production via excimer-mediated electron attachment to mixed rare gas/SF6 clusters

    NASA Astrophysics Data System (ADS)

    Foltin, M.; Rauth, T.; Märk, T. D.

    1992-08-01

    Electron attachment to mixed rare gas/SF6 clusters -- in contrast to pure SF6 clusters -- shows for the production of SF-6 ions, besides the zero energy resonance, an additional resonance peak at higher electron energies in the attachment cross-section function. The process of SF-6 production via this new resonance channel involves a multiple collision electron scavenging mechanism followed by an excimer-(R2*) induced decay of an intermediate complex ion (Rm·R2*SF-6 plus neutral products.

  11. Synthesis of covalently attached hexadecaanilines on carbon nanotubes: toward electronic nanocarbon preparation

    NASA Astrophysics Data System (ADS)

    Chiang, Long Y.; Anandakathir, Robinson; Hauck, Tanya S.; Lee, Lawrence; Canteenwala, Taizoon; Padmawar, Prashant A.; Pritzker, Kenneth; Bruno, Ferdinando F.; Samuelson, Lynne A.

    2010-04-01

    We describe the direct covalent-grafting synthesis of well-defined aniline oligomers, such as tetraaniline (A4) and hexadecaaniline (A16, major)/eicosaaniline (A20, minor), on the sidewalls of carbon nanotubes (CNTs), via dediazonization reaction, for achieving highly soluble nanomaterials suitable for printing purposes, with long-term physical stability. Chemically grafting a layer of electroactive hexadecaanilines on CNTs resembles semiconductive encapsulation of functionalized CNTs. The resulting covalent nanoconjugates SWNT-(A4)x, MWNT-(A4)x, SWNT-(A16/20)x, and MWNT-(A16/20)x were characterized by various spectroscopic and microscopic mapping methods. The combination of transmission electron microscopy (TEM) and electron energy loss spectroscopy (EELS) analyses provided direct evidence for A16/20 attachment to the CNTs, giving confirmation of the presence of heteroatoms surrounding the CNTs that was absent in the parent CNTs. Subsequent atom mapping in the vicinity of the tube structure allowed us to illustrate the 3D distribution of heteroatoms along the CNT surface.We describe the direct covalent-grafting synthesis of well-defined aniline oligomers, such as tetraaniline (A4) and hexadecaaniline (A16, major)/eicosaaniline (A20, minor), on the sidewalls of carbon nanotubes (CNTs), via dediazonization reaction, for achieving highly soluble nanomaterials suitable for printing purposes, with long-term physical stability. Chemically grafting a layer of electroactive hexadecaanilines on CNTs resembles semiconductive encapsulation of functionalized CNTs. The resulting covalent nanoconjugates SWNT-(A4)x, MWNT-(A4)x, SWNT-(A16/20)x, and MWNT-(A16/20)x were characterized by various spectroscopic and microscopic mapping methods. The combination of transmission electron microscopy (TEM) and electron energy loss spectroscopy (EELS) analyses provided direct evidence for A16/20 attachment to the CNTs, giving confirmation of the presence of heteroatoms surrounding the CNTs

  12. Equation-of-motion coupled cluster method for high spin double electron attachment calculations

    SciTech Connect

    Musiał, Monika Lupa, Łukasz; Kucharski, Stanisław A.

    2014-03-21

    The new formulation of the equation-of-motion (EOM) coupled cluster (CC) approach applicable to the calculations of the double electron attachment (DEA) states for the high spin components is proposed. The new EOM equations are derived for the high spin triplet and quintet states. In both cases the new equations are easier to solve but the substantial simplification is observed in the case of quintets. Out of 21 diagrammatic terms contributing to the standard DEA-EOM-CCSDT equations for the R{sub 2} and R{sub 3} amplitudes only four terms survive contributing to the R{sub 3} part. The implemented method has been applied to the calculations of the excited states (singlets, triplets, and quintets) energies of the carbon and silicon atoms and potential energy curves for selected states of the Na{sub 2} (triplets) and B{sub 2} (quintets) molecules.

  13. Unusual temperature dependence of the dissociative electron attachment cross section of 2-thiouracil.

    PubMed

    Kopyra, Janina; Abdoul-Carime, Hassan

    2016-01-21

    At low energies (<3 eV), molecular dissociation is controlled by dissociative electron attachment for which the initial step, i.e., the formation of the transient negative ion, can be initiated by shape resonance or vibrational Feshbach resonance (VFR) mediated by the formation of a dipole bound anion. The temperature dependence for shape-resonances is well established; however, no experimental information is available yet on the second mechanism. Here, we show that the dissociation cross section for VFRs mediated by the formation of a dipole bound anion decreases as a function of a temperature. The change remains, however, relatively small in the temperature range of 370-440 K but it might be more pronounced at the extended temperature range. PMID:26801033

  14. Negative ion resonances in carbon monoxide. Probing dissociative electron attachment in CO by velocity slice imaging

    NASA Astrophysics Data System (ADS)

    Gope, Krishnendu; Tadsare, Vishvesh; Prabhudesai, Vaibhav S.; Mason, Nigel J.; Krishnakumar, E.

    2016-06-01

    Dissociative electron attachment to CO leading to the formation of O- is studied using the velocity slice imaging technique. The angular distributions we obtained for the C(3P) and the C(1D) limits are found to be considerably different from a recent set of measurements [Tian et al., Phys. Rev. A 88, 012708 (2013); Wang et al., J. Chem. Phys. 143, 066101 (2015)] using a similar technique. The analysis of our results indicate incoherent contributions from states of Σ and Π symmetries to both these dissociation channels and rules out the need to invoke coherent excitation of several resonances, in contrast to what has been done in the above publications. We try to correlate these resonances to those observed in inelastic scattering and transmission experiments. We also confirm the presence of a third dissociation channel leading to C(1S) limit.

  15. Temperature dependence of the cross section for the fragmentation of thymine via dissociative electron attachment

    SciTech Connect

    Kopyra, Janina; Abdoul-Carime, Hassan

    2015-05-07

    Providing experimental values for absolute Dissociative Electron Attachment (DEA) cross sections for nucleobases at realistic biological conditions is a considerable challenge. In this work, we provide the temperature dependence of the cross section, σ, of the dehydrogenated thymine anion (T − H){sup −} produced via DEA. Within the 393-443 K temperature range, it is observed that σ varies by one order of magnitude. By extrapolating to a temperature of 313 K, the relative DEA cross section for the production of the dehydrogenated thymine anion at an incident energy of 1 eV decreases by 2 orders of magnitude and the absolute value reaches approximately 6 × 10{sup −19} cm{sup 2}. These quantitative measurements provide a benchmark for theoretical prediction and also a contribution to a more accurate description of the effects of ionizing radiation on molecular medium.

  16. s-wave threshold in electron attachment - Observations and cross sections in CCl4 and SF6 at ultralow electron energies

    NASA Technical Reports Server (NTRS)

    Chutjian, A.; Alajajian, S. H.

    1985-01-01

    The threshold photoionization method was used to study low-energy electron attachment phenomena in and cross sections of CCl4 and SF6 compounds, which have applications in the design of gaseous dielectrics and diffuse discharge opening switches. Measurements were made at electron energies from below threshold to 140 meV at resolutions of 6 and 8 meV. A narrow resolution-limited structure was observed in electron attachment to CCl4 and SF6 at electron energies below 10 meV, which is attributed to the divergence of the attachment cross section in the limit epsilon, l approaches zero. The results are compared with experimental collisional-ionization results, electron-swarm unfolded cross sections, and earlier threshold photoionization data.

  17. Experimental and modeling study of thermal rate coefficients and cross sections for electron attachment to C(60).

    PubMed

    Viggiano, Albert A; Friedman, Jeffrey F; Shuman, Nicholas S; Miller, Thomas M; Schaffer, Linda C; Troe, Jürgen

    2010-05-21

    Thermal electron attachment to C(60) has been studied by relative rate measurements in a flowing afterglow Langmuir probe apparatus. The rate coefficients of the attachment k(1) are shown to be close to 10(-6) cm(3) s(-1) with a small negative temperature coefficient. These results supersede measurements from the 1990s which led to much smaller values of k(1) with a large positive temperature coefficient suggesting an activation barrier. Theoretical modeling of k(1) in terms of generalized Vogt-Wannier capture theory shows that k(1) now looks more consistent with measurements of absolute attachment cross sections sigma(at) than before. The comparison of capture theory and experimental rate or cross section data leads to empirical correction factors, accounting for "intramolecular vibrational relaxation" or "electron-phonon coupling," which reduce k(1) below the capture results and which, on a partial wave-selected level, decrease with increasing electron energy. PMID:20499963

  18. Rare reaction channels in real-time time-dependent density functional theory: the test case of electron attachment

    NASA Astrophysics Data System (ADS)

    Lacombe, Lionel; Dinh, P. Huong Mai; Reinhard, Paul-Gerhard; Suraud, Eric; Sanche, Leon

    2015-08-01

    We present an extension of standard time-dependent density functional theory (TDDFT) to include the evaluation of rare reaction channels, taking as an example of application the theoretical modelling of electron attachment to molecules. The latter process is of great importance in radiation-induced damage of biological tissue for which dissociative electron attachment plays a decisive role. As the attachment probability is very low, it cannot be extracted from the TDDFT propagation whose mean field provides an average over various reaction channels. To extract rare events, we augment TDDFT by a perturbative treatment to account for the occasional jumps, namely electron capture in our test case. We apply the modelling to electron attachment to H2O, H3O+, and (H2O)2. Dynamical calculations have been done at low energy (3-16 eV). We explore, in particular, how core-excited states of the targets show up as resonances in the attachment probability. Contribution to the Topical Issue "COST Action Nano-IBCT: Nano-scale Processes Behind Ion-Beam Cancer Therapy", edited by Andrey Solov'yov, Nigel Mason, Gustavo García, Eugene Surdutovich.

  19. Cross sections for 14-eV e-H{sub 2} resonant collisions: Dissociative electron attachment

    SciTech Connect

    Celiberto, R.; Janev, R. K.; Wadehra, J. M.; Laricchiuta, A.

    2009-07-15

    The dissociative electron attachment (DEA) process in electron-H{sub 2} molecule collisions, involving the {sup 2}{sigma}{sub g}{sup +} excited electronic Rydberg state of molecular hydrogen ion H{sub 2}{sup -}, is investigated theoretically. The DEA cross section has been calculated within the local complex potential approximation. The convoluted cross section, which presents a peak located at the incident energy of about 14 eV, compares favorably with available experimental data.

  20. Dissociative electron attachment and vibrational excitation of CF{sub 3}Cl: Effect of two vibrational modes revisited

    SciTech Connect

    Tarana, Michal; Houfek, Karel; Horacek, Jiri; Fabrikant, Ilya I.

    2011-11-15

    We present a study of dissociative electron attachment and vibrational excitation processes in electron collisions with the CF{sub 3}Cl molecule. The calculations are based on the two-dimensional nuclear dynamics including the C-Cl symmetric stretch coordinate and the CF{sub 3} symmetric deformation (umbrella) coordinate. The complex potential energy surfaces are calculated using the ab initio R-matrix method. The results for dissociative attachment and vibrational excitation of the umbrella mode agree quite well with experiment whereas the cross section for excitation of the C-Cl symmetric stretch vibrations is about a factor-of-three too low in comparison with experimental data.

  1. Synthesis of covalently attached hexadecaanilines on carbon nanotubes: toward electronic nanocarbon preparation.

    PubMed

    Chiang, Long Y; Anandakathir, Robinson; Hauck, Tanya S; Lee, Lawrence; Canteenwala, Taizoon; Padmawar, Prashant A; Pritzker, Kenneth; Bruno, Ferdinando F; Samuelson, Lynne A

    2010-04-01

    We describe the direct covalent-grafting synthesis of well-defined aniline oligomers, such as tetraaniline (A(4)) and hexadecaaniline (A(16), major)/eicosaaniline (A(20), minor), on the sidewalls of carbon nanotubes (CNTs), via dediazonization reaction, for achieving highly soluble nanomaterials suitable for printing purposes, with long-term physical stability. Chemically grafting a layer of electroactive hexadecaanilines on CNTs resembles semiconductive encapsulation of functionalized CNTs. The resulting covalent nanoconjugates SWNT-(A(4))(x), MWNT-(A(4))(x), SWNT-(A(16/20))(x), and MWNT-(A(16/20))(x) were characterized by various spectroscopic and microscopic mapping methods. The combination of transmission electron microscopy (TEM) and electron energy loss spectroscopy (EELS) analyses provided direct evidence for A(16/20) attachment to the CNTs, giving confirmation of the presence of heteroatoms surrounding the CNTs that was absent in the parent CNTs. Subsequent atom mapping in the vicinity of the tube structure allowed us to illustrate the 3D distribution of heteroatoms along the CNT surface. PMID:20644756

  2. Kinetics of low energy electron attachment to some fluorinated alcohols in the gas phase

    NASA Astrophysics Data System (ADS)

    Wnorowski, K.; Wnorowska, J.; Kopyra, J.; Michalczuk, B.; Szamrej, I.; Barszczewska, W.

    2014-01-01

    Thermal electron attachment processes in the mixtures of CH3CH2OH, CF3CH2OH, CF3CF2CH2OH, (CF3)2CHOH and CH3CH(OH)CF3 with carbon dioxide have been investigated using an electron Pulsed Townsend technique. Measurements were carried out in the temperature range (298-413) K. The obtained rate coefficients depended on temperature in accordance to Arrhenius equation. From the fit to the experimental data points with function ln(k) = ln(A)-Ea/kBT the activation energies (Ea's) were determined. The rate coefficients at 298 K are equal to 3.2 × 10-13 cm3 s-1, 5.1 × 10-11 cm3 s-1, 1.1 × 10-10 cm3 s-1, 3.0 × 10-10 cm3 s-1 and 2.6 × 10-11 cm3 s-1 and activation energies are: 0.37 eV, 0.25 eV, 0.28 eV, 0.20 eV and 0.23 eV, respectively for CH3CH2OH, CF3CH2OH, CF3CF2CH2OH, (CF3)2CHOH and CH3CH(OH)CF3.

  3. Oxidant enhancement in martian dust devils and storms: storm electric fields and electron dissociative attachment.

    PubMed

    Delory, Gregory T; Farrell, William M; Atreya, Sushil K; Renno, Nilton O; Wong, Ah-San; Cummer, Steven A; Sentman, Davis D; Marshall, John R; Rafkin, Scot C R; Catling, David C

    2006-06-01

    Laboratory studies, numerical simulations, and desert field tests indicate that aeolian dust transport can generate atmospheric electricity via contact electrification or "triboelectricity." In convective structures such as dust devils and dust storms, grain stratification leads to macroscopic charge separations and gives rise to an overall electric dipole moment in the aeolian feature, similar in nature to the dipolar electric field generated in terrestrial thunderstorms. Previous numerical simulations indicate that these storm electric fields on Mars can approach the ambient breakdown field strength of approximately 25 kV/m. In terrestrial dust phenomena, potentials ranging from approximately 20 to 160 kV/m have been directly measured. The large electrostatic fields predicted in martian dust devils and storms can energize electrons in the low pressure martian atmosphere to values exceeding the electron dissociative attachment energy of both CO2 and H2O, which results in the formation of the new chemical products CO/O- and OH/H-, respectively. Using a collisional plasma physics model, we present calculations of the CO/O- and OH/H- reaction and production rates. We demonstrate that these rates vary geometrically with the ambient electric field, with substantial production of dissociative products when fields approach the breakdown value of approximately 25 kV/m. The dissociation of H2O into OH/H- provides a key ingredient for the generation of oxidants; thus electrically charged dust may significantly impact the habitability of Mars. PMID:16805701

  4. A Nonlocal Model of Dissociative Electron Attachment andVibrational Excitation of NO

    SciTech Connect

    Trevisan, Cynthia S.; Houfek, Karel; Zhang, Z.; Orel, Ann E.; McCurdy, C. William; Rescigno, Thomas N.

    2005-01-01

    We present the results of a study of elastic scattering and vibrational excitation of NO by electron impact in the low-energy (0-2eV) region where the cross sections are dominated by resonance contributions. The {sup 3}{Sigma}{sup -}, {sup 1}{Delta} and {sup 1}{Sigma}{sup +} NO{sup -} resonance lifetimes are taken from our earlier study [Phys. Rev. A 69, 062711(2004)], but the resonance energies used here are obtained from new configuration-interaction studies. Here we employ a more elaborate nonlocal treatment of the nuclear dynamics, which is found to remedy the principal deficiencies of the local complex potential model we employed in our earlier study, and gives cross sections in better agreement with the most recent experiments. We also present cross sections for dissociative electron attachment to NO leading to ground state products, O{sup -}({sup 2}P) + N({sup 4}S). The calculations show that, while the peak cross sections starting from NO in its ground vibrational state are very small ({approx} 10{sup -20}cm{sup 2}), the cross sections are extremely sensitive to vibrational excitation of the target and should be readily observable for target NO molecules excited to {nu} = 10 and above.

  5. A nonlocal, ab initio model of dissociative electron attachment and vibrational excitation of NO

    SciTech Connect

    Trevisan, Cynthia S.; Houfek, Karel; Zhang, Zhiyong; Orel, Ann E.; McCurdy, C. William; Rescigno, Thomas N.

    2005-02-01

    We present the results of an ab initio study of elastic scattering and vibrational excitation of NO by electron impact in the low-energy (0-2 eV) region where the cross sections are dominated by resonance contributions. The 3Sigma-, 1Delta and 1Sigma+ NO- resonance lifetimes are taken from our earlier study [Phys. Rev. A 69, 062711 (2004)], but the resonance energies used here are obtained from new configuration-interaction studies. Here we employ a more elaborate nonlocal treatment of the nuclear dynamics, which is found to remedy the principal deficiencies of the local complex potential model we employed in our earlier study, and gives cross sections in better agreement with the most recent experiments. We also present cross sections for dissociative electron attachment to NO leading to groundstate products. The calculations show that, while the peak cross sections starting from NO in its ground vibrational state are very small, the cross sections are extremely sensitive to vibrational excitation of the target and should be readily observable for target NO molecules excited to v = 10 and above.

  6. Dissociative electron attachment to the H2O molecule II: nucleardynamics on coupled electronic surfaces within the local complexpotential model

    SciTech Connect

    Haxton, Daniel J.; Rescigno, Thomas N.; McCurdy, C. William

    2006-12-21

    We report the results of a first-principles study of dissociative electron attachment (DEA) to H{sub 2}O. The cross sections were obtained from nuclear dynamics calculations carried out in full dimensionality within the local complex potential model by using the multi-configuration time-dependent Hartree method. The calculations employ our previously obtained global, complex-valued, potential energy surfaces for the three ({sup 2}B{sub 1}, {sup 2}A{sub 1}, and {sup 2}B{sub 2}) electronic Feshbach resonances involved in this process. These three metastable states of H{sub 2}O{sup -} undergo several degeneracies, and we incorporate both the Renner-Teller coupling between the {sup 2}B{sub 1} and {sup 2}A{sub 1} states, as well as the conical intersection between the {sup 2}A{sub 1} and {sup 2}B{sub 2} states, into our treatment. The nuclear dynamics are inherently multi-dimensional and involve branching between different final product arrangements as well as extensive excitation of the diatomic fragment. Our results successfully mirror the qualitative features of the major fragment channels observed, but are less successful in reproducing the available results for some of the minor channels. We comment on the applicability of the local complex potential model to such a complicated resonant system.

  7. Direct measurement of the characteristic three-body electron attachment time in the atmospheric air in direct current electric field

    SciTech Connect

    Shutov, A. V.; Smetanin, I. V.; Ionin, A. A.; Levchenko, A. O.; Seleznev, L. V.; Sinitsyn, D. V.; Ustinovskii, N. N.; Zvorykin, V. D.

    2013-07-15

    We report the results of theoretical and experimental study of the characteristic time for three-body attachment of electrons produced by 100 fs UV laser pulse in the atmosphere air in the external DC electric field ranged from 0.2 to 10 kV/cm.

  8. 46 CFR 67.218 - Optional filing of instruments in portable document format as attachments to electronic mail.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... recording under § 67.200 may be submitted in portable document format (.pdf) as an attachment to electronic... submitted for filing in .pdf format pertains to a vessel that is not a currently documented vessel, a... with the National Vessel Documentation Center or must be submitted in .pdf format with the...

  9. Analytical model for rates of electron attachment and intramolecular electron transfer in electron transfer dissociation mass spectrometry.

    PubMed

    Simons, Jack

    2010-05-26

    A new physical model is put forth to allow the prediction of electron transfer rates and distances for (i) intramolecular transfer from an n > or = 3 Rydberg orbital on a positive site to a disulfide or amide bond site and (ii) intermolecular transfer from an anion donor to an n > or = 3 Rydberg orbital of a positively charged polypeptide. Although ab initio methods have proven capable of handling such electron transfer events when the Rydberg orbital has principal quantum number n = 3, they have proven to be incapable of handling Rydberg states having quantum number n > 3, so having a new tool capable of handling n > 3 Rydberg states is important. The model (i) focuses on each Rydberg orbital's large peak of high amplitude, (ii) approximates the electron density within this peak as constant within a radial shell characterized by a radius and thickness T both of which depend on the quantum number n, and (iii) assumes that strong coupling (either with an orbital of an anion donor or to a disulfide sigma* or a backbone amide pi* orbital) occurs when the valence orbital penetrates fully within the radial shell of the Rydberg orbital. These assumptions permit a derivation of the ratios of rates of electron transfer for n > 3 to those for n = 3. Combining these ratios with ab initio rates for n = 3 allows one to make rate predictions for inter- and intramolecular electron transfer involving Rydberg orbitals appropriate to the electron transfer dissociation process. One important prediction of this model is that the combination of large-penetration and Landau-Zener surface-crossing conditions places very severe limitations on which Rydberg levels can initially be populated in electron transfer dissociation. Another prediction is that a Rydberg orbital of a given principal quantum number n has a limited range of distances over which it can transfer an electron; sigma* or pi* orbitals either too far from or too close to a given Rydberg orbital cannot accept an electron

  10. Formation of carbon chain molecular anions by radiative electron attachment and their destruction by photodetachment

    NASA Astrophysics Data System (ADS)

    Khamesian, Marjan; Douguet, Nicolas; Raoult, Maurice; Dulieu, Olivier; Kokoouline, Viatcheslav

    2016-05-01

    Several negative ions Cn H- (n = 4 , 6 , 8), Cn N- (n = 1 , 3 , 5) have been recently observed in the interstellar medium (ISM). A possible mechanism of formation is radiative electron attachment (REA). In this study we develop a first principle theoretical approach to study the REA and apply the approach to the formation of the negative molecular ions CN-, C2 H-, C3 N-, C4 H-, C5 N-, C6 H-, and C8 H-. The theoretical approach is based on the UK R-matrix calculations. Cross sections and rate coefficients for formation of these ions by REA to the corresponding neutral radicals are calculated. There is no experimental data on REA of these ions. However, using a similar approach we have also calculated cross sections for photodetachment of the negative ions and compared the obtained results with available experimental data. The good agreement with photodetachment experimental data provides a confirmation that the REA cross sections obtained in this study is also reliable. NSF Grant PHYS-1506391.

  11. Gas Phase Dissociative Electron Attachment to Formamide Derivatives NMF and DMF

    NASA Astrophysics Data System (ADS)

    Li, Zhou; Dawley, M. Michele; Ptasinska, Sylwia

    2015-09-01

    Fragmentation of biomolecules, such as nucleobases, induced by low energy electrons can lead to the break of DNA strands. Dissociative electron attachment (DEA), which can occur due to low energy interactions, is initiated with the formation of transient negative ions which exhibit characteristic resonant profiles in the product ion yield. The consequent fragmentation process can either be as simple as a single bond cleavage or a relatively complex process involving multiple bond rearrangements. Measurements of resonant peaks in ion yields and identification of ion products provide information of the resonant energies of the parent molecules as well as the fragmentation pathways. N-methylformamide (NMF) and dimethylformamide (DMF) are both derivatives of formamide which is the simplest structure containing the peptide bond linkage. In this work we identified anion fragments and measured resonance profiles of produced anions due to DEA to NMF and DMF. The anionic species produced from the two molecules were compared as well as the resonant positions and ion yields. Based on this comparison, the DEA process to the two molecules bears similarities such as leading to breaking of peptide bonds (C-N), as well as discrepancies such as absence of OCN- in DEA to DMF. The selective property of H atom loss, which is reported in the DEA to formamide, is also justified in our experiment since no dehydrogenated DMF anion was detected. This material is based upon work supported by the U.S. Department of Energy Office of Science, Office of Basic Energy Sciences under Award Number DE-FC02-04ER15533.

  12. High-order determinantal equation-of-motion coupled-cluster calculations for ionized and electron-attached states

    NASA Astrophysics Data System (ADS)

    Hirata, So; Nooijen, Marcel; Bartlett, Rodney J.

    2000-10-01

    General-order equation-of-motion coupled-cluster methods for ionization potentials and electron affinities (IP-EOM-CC and EA-EOM-CC) are developed by employing a determinantal algorithm. With these, principal ionization potentials or electron affinities of diatomic molecules and the excitation energies of their ionized or electron-attached counterparts are computed across different approximations of the cluster operator and the ionization (electron-attachment) operator. IP-EOM-CC(2,2h-1p)=IP-EOM-CCSD and EA-EOM-CC(2,1h-2p)=EA-EOM-CCSD or EA-EOM-CC(2,2h-3p) prove to be well-balanced models for principal ionization potentials and electron affinities, whereas for the quantitative descriptions of non-Koopmans ionization or electron-attachment processes IP-EOM-CC(3,3h-2p)=IP-EOM-CCSDT and EA-EOM-CC(2,2h-3p) appear to be the minimal levels.

  13. Negative-ion formation in the explosives RDX, PETN, and TNT using the Reversal Electron Attachment Detection (READ) technique

    NASA Technical Reports Server (NTRS)

    Chutijian, Ara; Boumsellek, S.; Alajajian, S. H.

    1992-01-01

    In the search for high sensitivity and direct atmospheric sampling of trace species, techniques have been developed such as atmospheric-sampling, glow-discharge ionization (ASGDI), corona discharge, atmospheric pressure ionization (API), electron-capture detection (ECD), and negative-ion chemical ionization (NICI) that are capable of detecting parts-per-billion to parts-per-trillion concentrations of trace species. These techniques are based on positive- or negative-ion formation via charge-transfer to the target, or electron capture under multiple-collision conditions in a Maxwellian distribution of electron energies at the source temperature. One drawback of the high-pressure, corona- or glow-discharge devices is that they are susceptible to interferences either through indistinguishable product masses, or through undesired ion-molecule reactions. The ASGDI technique is relatively immune from such interferences, since at target concentrations of less than 1 ppm the majority of negative ions arises via electron capture rather than through ion-molecule chemistry. A drawback of the conventional ECD, and possibly of the ASGDI, is that they exhibit vanishingly small densities of electrons with energies in the range 0-10 millielectron volts (meV), as can be seen from a typical Maxwellian electron energy distribution function at T = 300 K. Slowing the electrons to these subthermal (less than 10 meV) energies is crucial, since the cross section for attachment of several large classes of molecules is known to increase to values larger than 10(exp -12) sq cm at near-zero electron energies. In the limit of zero energy these cross sections are predicted to diverge as epsilon(exp -1/2), where epsilon is the electron energy. In order to provide a better 'match' between the electron energy distribution function and attachment cross section, a new concept of attachment in an electrostatic mirror was developed. In this scheme, electrons are brought to a momentary halt by

  14. Cross sections for 14-eV e-H{sub 2} resonant collisions: Isotope effect in dissociative electron attachment

    SciTech Connect

    Celiberto, R.; Janev, R. K.; Wadehra, J. M.; Laricchiuta, A.

    2011-07-15

    The process of dissociative attachment of electrons to molecular hydrogen and its isotopes in the energy range at approximately 14 eV is investigated. The dissociative electron attachment cross sections for all six hydrogen isotopes are calculated over an extended range of electron energies using the local complex potential model with the excited Rydberg {sup 2}{Sigma}{sub g}{sup +} electronic state of H{sub 2}{sup -} acting as the intermediate resonant state. A significant isotope effect in theoretical electron attachment cross sections is observed, in agreement with previous predictions and experimental observations. A two-parameter analytic expression for the cross section is derived from the theory that fits accurately the numerically calculated cross sections for all isotopes. Similarly, an analytic mass-scaling relation is derived from the theory that accurately reproduces the numerically calculated rate coefficients for all isotopes in the 0.1-1000 eV temperature range by using the rate coefficient for the H{sub 2} isotope only. The latter is represented by an analytic fit expression with two parameters only.

  15. Theoretical study of pressure dependence of transition temperature of In and Pb

    SciTech Connect

    Kumar, Priyank; Bhatt, N. K.; Vyas, P. R.; Gohel, V. B.

    2015-08-28

    Recently proposed structured local pseudopotential (PP) by Fiolhais et al. has been successfully used to compute superconducting state parameters (SSP): electron-phonon coupling strength (λ), Coulomb pseudopotential (μ*), critical temperature (T{sub c}), effective interaction strength (N{sub 0}V), isotopic effect parameter (α) and their pressure dependence of non-transition metals In and Pb as a test case. Pressure dependence of the Debye temperature has been computed by Gruneisen model. Present results are in good agreement with experimental and other theoretical results. Present study has been further extended to estimate volume (critical volume) at which λ=μ*, where Tc and N{sub 0}V becomes zero. The presently used model is found to be transferable at the extreme environment without any adjustment of parameters further alongwith its simplicity and predictivity.

  16. The influence of the temperature on electron attachment to some Br-substituted alkanes

    NASA Astrophysics Data System (ADS)

    Wnorowski, K.; Wnorowska, J.; Michalczuk, B.; Jówko, A.; Barszczewska, W.

    2013-10-01

    Thermal electron attachment rate coefficients and activation energies for CH3CH2Br, CH3CH2CH2Br, CH3CHBrCH3, CF3CHBrCH3, CH3(CH2)2CH2Br and CH2F(CH2)2CH2Br have been measured using the Pulsed Townsend technique over the temperature range (298-378) K. The corresponding rate coefficients (k's) at 298 K were equal to 9.3 ± 2.10 × 10-13, 2.9 ± 0.20 × 10-12, 2.7 ± 0.07 × 10-12, 1.1 ± 0.06 × 10-9, 6.6 ± 1.10 × 10-12 and 2.3 ± 0.3 × 10-10 cm3s-1, respectively. Activation energies (Ea's) were determined from the fit of the Arrhenius function to the experimental points and were found to be equal to 0.35 ± 0.002, 0.35 ± 0.004, 0.31 ± 0.004, 0.19 ± 0.002, 0.33 ± 0.006 and 0.22 ± 0.002 eV, respectively for CH3CH2Br, CH3CH2CH2Br, CH3CHBrCH3, CF3CHBrCH3, CH3(CH2)2CH2Br and CH2F(CH2)2CH2Br molecules.

  17. Mechanistic investigation on pressure dependency of Heckel parameter.

    PubMed

    Patel, Sarsvatkumar; Kaushal, Aditya Mohan; Bansal, Arvind Kumar

    2010-04-15

    This work proposed to study the influence of varying compaction pressure on the plastic energy, elasticity (Young's modulus), particle yield strength, strain hardening, and applied pressures on derived Heckel parameter using material with different densification and deformation mechanisms: ibuprofen (IBN), paracetamol (PCM) (elastic behavior), methyl cellulose (Me-Cel), microcrystalline cellulose (MCC), sodium chloride (NaCl) (plastic behavior), and dicalcium phosphate (DCP) (brittle fracture). Force-displacement data were captured during in-die compaction for all materials having different deformation behavior. The apparent mean yield pressure (Py), plastic energy, Young's moduli, strain hardening parameter and rate of increase in Py were calculated from force-displacement compaction profiles obtained across a pressure range of 65-260 MPa. Materials under confined compression loading showed pressure dependent biphasic behavior in Py upon increasing pressure from 65 MPa to 260 MPa. IBN and PCM showed pressure dependency due to simultaneous elasticity and strain hardening upon increasing applied pressure. Me-Cel, MCC, and NaCl showed lower pressure dependency while DCP showed higher change in Py upon increasing pressure as a result of higher yield strength of DCP particles. Apparent mean yield pressure from Heckel analysis was significantly affected by the applied pressure, viscoelastic behavior, particle yield strength, and strain hardening. The simultaneously occurring events of elastic deformation and strain hardening give a false increase in Py at higher applied pressures. PMID:20083173

  18. s-wave threshold in electron attachment - Results in 2-C4F6 and CFCl3 at ultra-low electron energies

    NASA Technical Reports Server (NTRS)

    Chutjian, A.; Alajajian, S. H.; Ajello, J. M.; Orient, O. J.

    1984-01-01

    Electron attachment lineshapes and cross sections are reported for the processes 2-C4F6(-)/2-C4F6 and Cl(-)/CFCl3 at electron energies of 0-120 and 0-140 meV, and at resolutions of 6 and 7 meV (FWHM), respectively. As in previous measurements in CCl4 and SF6, the results show resolution-limited narrow structure in the cross section at electron energies below 15 meV. This structure arises from the divergence of the s-wave cross section in the limit of zero electron energy. Comparisons are given with swarm-measured results, and with collisional ionization (high-Rydberg attachment) data in this energy range.

  19. Pressure dependence of the Fermi surface of hcp Yb

    NASA Astrophysics Data System (ADS)

    Schirber, J. E.; Beaudry, B. J.; Jepsen, O.

    1981-06-01

    The pressure dependence of Fermi-surface cross sections for principal symmetry directions has been investigated using solid He pressure generation techniques. Careful searches for de Haas-van Alphen signals were conducted from 2 to 9 kbar in both virgin fcc crystals and samples transformed from hcp to fcc. No sign of the frequency reported by Ribault was detected. Results are discussed in terms of theoretically calculated pressure-induced changes in the band structure and Fermi surface of the hcp phase of Yb.

  20. Comparative electron paramagnetic resonance investigation of reduced graphene oxide and carbon nanotubes with different chemical functionalities for quantum dot attachment

    NASA Astrophysics Data System (ADS)

    Pham, Chuyen V.; Krueger, Michael; Eck, Michael; Weber, Stefan; Erdem, Emre

    2014-03-01

    Electron paramagnetic resonance (EPR) spectroscopy has been applied to different chemically treated reduced graphene oxide (rGO) and multiwalled carbon nanotubes (CNTs). A narrow EPR signal is visible at g = 2.0029 in both GO and CNT-Oxide from carbon-related dangling bonds. EPR signals became broader and of lower intensity after oxygen-containing functionalities were reduced and partially transformed into thiol groups to obtain thiol-functionalized reduced GO (TrGO) and thiol-functionalized CNT (CNT-SH), respectively. Additionally, EPR investigation of CdSe quantum dot-TrGO hybrid material reveals complete quenching of the TrGO EPR signal due to direct chemical attachment and electronic coupling. Our work confirms that EPR is a suitable tool to detect spin density changes in different functionalized nanocarbon materials and can contribute to improved understanding of electronic coupling effects in nanocarbon-nanoparticle hybrid nano-composites promising for various electronic and optoelectronic applications.

  1. Pressure dependence of glass transition temperature of elastomeric glasses

    NASA Astrophysics Data System (ADS)

    Pae, K. D.; Tang, C.-L.; Shin, E.-S.

    1984-11-01

    The pressure dependence of the glass transition temperature Tg of two elastomers, Solithane 113 and 3,3-bis(azidomethyl)oxetane/tetrahydrofuran (BAMO/THF) has been determined, employing high-pressure differential thermal analysis (HP-DTA) and dielectric techniques, up to 8.5 kbar. The glasses of the elastomers were named the specific (or Pi glass) or the general glass depending on how the glasses were formed. A Pi glass was formed by lowering temperature under a constant pressure (Pi) and the pressure dependency of the Pi glass was determined after changing pressure only in the glassy state. The general glass consists of a series of specific glasses but the Tg is determined only at pressures under which the glass is formed. The Tg for both glasses increased with increasing pressure. However, the Tg for the Pi glass appears to level off at very high pressures while the Tg does not level off for the general glass. Thermodynamic analysis was made to show that for many general glasses dTg/dP=Δβ/(1+n)Δα holds, in which n=1 for Solithane and many other glasses. It is also shown that a modified Gibbs and DiMarzio theory can be used effectively to predict the observed experimental results.

  2. Pressure dependence of the charge-density-wave gap in rare-earth tritellurides.

    PubMed

    Sacchetti, A; Arcangeletti, E; Perucchi, A; Baldassarre, L; Postorino, P; Lupi, S; Ru, N; Fisher, I R; Degiorgi, L

    2007-01-12

    We investigate the pressure dependence of the optical properties of CeTe3, which exhibits an incommensurate charge-density-wave (CDW) state already at 300 K. Our data are collected in the midinfrared spectral range at room temperature and at pressures between 0 and 9 GPa. The energy for the single particle excitation across the CDW gap decreases upon increasing the applied pressure, similarly to the chemical pressure by rare-earth substitution. The broadening of the bands upon lattice compression removes the perfect nesting condition of the Fermi surface and therefore diminishes the impact of the CDW transition on the electronic properties of RTe3. PMID:17358625

  3. CARBON-RICH MOLECULAR CHAINS IN PROTOPLANETARY AND PLANETARY ATMOSPHERES: QUANTUM MECHANISMS AND ELECTRON ATTACHMENT RATES FOR ANION FORMATION

    SciTech Connect

    Carelli, F.; Grassi, T.; Gianturco, F. A.; Satta, M.

    2013-09-10

    The elementary mechanisms through which molecular polyynes could form stable negative ions after interacting with free electrons in planetary atmospheres (e.g., Titan's) are analyzed using quantum scattering calculations and quantum structure methods. The case of radical species and of nonpolar partners are analyzed via specific examples for both the C{sub n}H and HC{sub n}H series, with n values from 4 to 12. We show that attachment processes to polar radicals are dominating the anionic production and that the mediating role of dipolar scattering states is crucial to their formation. The corresponding attachment rates are presented as calculated upper limits to their likely values and are obtained down to the low temperatures of interest. The effects of the computed rates, when used in simple evolutionary models, are also investigated and presented in detail.

  4. Pressure dependence of local vibrational modes in InP

    SciTech Connect

    McCluskey, M. D.; Zhuravlev, K. K.; Davidson, B. R.; Newman, R. C.

    2001-03-15

    Using infrared spectroscopy and a diamond-anvil cell, we have observed carbon and carbon-hydrogen local vibrational modes (LVM's) in InP at hydrostatic pressures as high as 5.5 GPa at liquid-helium temperatures. For pressures beyond 4.5 GPa, the carbon-hydrogen mode was not observed, perhaps as a result of a transformation of the complex into a different configuration. The LVM arising from carbon substitutional impurities varies linearly with pressure, whereas the shift of the carbon-hydrogen mode has a positive curvature. Both of these observations are in qualitative agreement with the pressure dependence of LVM's in GaAs. While the substitutional carbon impurities show very similar pressure shifts in the two materials, the linear pressure coefficient of the carbon-hydrogen stretch mode in InP is nearly three times that in GaAs. For all the measured modes, the Gru''neisen parameters increase with pressure.

  5. Pressure-dependent isotopic composition of iron alloys

    NASA Astrophysics Data System (ADS)

    Shahar, A.; Schauble, E. A.; Caracas, R.; Gleason, A. E.; Reagan, M. M.; Xiao, Y.; Shu, J.; Mao, W.

    2016-04-01

    Our current understanding of Earth’s core formation is limited by the fact that this profound event is far removed from us physically and temporally. The composition of the iron metal in the core was a result of the conditions of its formation, which has important implications for our planet’s geochemical evolution and physical history. We present experimental and theoretical evidence for the effect of pressure on iron isotopic composition, which we found to vary according to the alloy tested (FeO, FeHx, or Fe3C versus pure Fe). These results suggest that hydrogen or carbon is not the major light-element component in the core. The pressure dependence of iron isotopic composition provides an independent constraint on Earth’s core composition.

  6. Pressure dependence of the melting temperature of metals

    NASA Technical Reports Server (NTRS)

    Schlosser, Herbert; Vinet, Pascal; Ferrante, John

    1989-01-01

    A new method for the analysis of the experimental data for the pressure dependence of the melting temperature of metals is presented. The method combines Lindemann's law, the Debye model, and a first-order equation of state with the experimental observation that the Grueneisen parameter divided by the volume is constant. It is observed that, based on these assumptions, in the absence of phase transitions, plots of the logarithm of the normalized melting temperature versus the logarithm of the normalized pressure are straight lines. It is found that the normalized-melting--temperature versus normalized-pressure curves accurately satisfy the linear relationship for Al, Ag, Au, Cs, Cu, K, Na, Pt, and Rb. In addition, this technique provides a sensitive tool for detecting phase transitions.

  7. Pressure-dependent isotopic composition of iron alloys.

    PubMed

    Shahar, A; Schauble, E A; Caracas, R; Gleason, A E; Reagan, M M; Xiao, Y; Shu, J; Mao, W

    2016-04-29

    Our current understanding of Earth's core formation is limited by the fact that this profound event is far removed from us physically and temporally. The composition of the iron metal in the core was a result of the conditions of its formation, which has important implications for our planet's geochemical evolution and physical history. We present experimental and theoretical evidence for the effect of pressure on iron isotopic composition, which we found to vary according to the alloy tested (FeO, FeH(x), or Fe3C versus pure Fe). These results suggest that hydrogen or carbon is not the major light-element component in the core. The pressure dependence of iron isotopic composition provides an independent constraint on Earth's core composition. PMID:27126042

  8. Fragmentation of deprotonated d-ribose and d-fructose in MALDI--Comparison with dissociative electron attachment

    NASA Astrophysics Data System (ADS)

    Bald, Ilko; Flosadóttir, Helga D.; Kopyra, Janina; Illenberger, Eugen; Ingólfsson, Oddur

    2009-02-01

    We present a detailed, collaborative study on the fragmentation of deprotonated native d-ribose and d-fructose and the isotopically labelled 1-13C-d-ribose, 5-13C-d-ribose and C-1-d-d-ribose. The fragmentation is studied in a matrix assisted laser desorption/ionization time of flight mass spectrometer (MALDI ToF MS), both in in-source decay (ISD) and post-source decay (PSD) mode and compared with fragmentation through dissociative electron attachment (DEA). Fragmentation of deprotonated monosaccharides formed in the MALDI process, as well as their transient molecular anions formed upon electron attachment are characterized by loss of different numbers of H2O and CH2O units. Two different fragmentation pathways leading to cross-ring cleavage are identified. Metastable decay of deprotonated d-ribose proceeds either via an X-type cleavage yielding fragment anions at m/z = 119, 100 and 89, or via an A-type cleavage resulting in m/z = 89, 77 and 71. A fast and early metastable cross-ring cleavage of deprotonated d-ribose observed in in-source decay is dominated by X-type cleavage leading mainly to m/z = 100 and 71. For dissociative electron attachment to d-ribose a sequential dissociation was identified that includes metastable decay of the dehydrogenated molecular anion leading to m/z = 89. All other fragmentation reactions in DEA to d-ribose are likely to proceed directly and on a faster timescale (below 400 ns).

  9. Theoretical study of radiative electron attachment to CN, C{sub 2}H, and C{sub 4}H radicals

    SciTech Connect

    Douguet, Nicolas; Fonseca dos Santos, S.; Orel, Ann E.; Raoult, Maurice; Dulieu, Olivier

    2015-06-21

    A first-principle theoretical approach to study the process of radiative electron attachment is developed and applied to the negative molecular ions CN{sup −}, C{sub 4}H{sup −}, and C{sub 2}H{sup −}. Among these anions, the first two have already been observed in the interstellar space. Cross sections and rate coefficients for formation of these ions by direct radiative electron attachment to the corresponding neutral radicals are calculated. For the CN molecule, we also considered the indirect pathway, in which the electron is initially captured through non-Born-Oppenheimer coupling into a vibrationally resonant excited state of the anion, which then stabilizes by radiative decay. We have shown that the contribution of the indirect pathway to the formation of CN{sup −} is negligible in comparison to the direct mechanism. The obtained rate coefficients for the direct mechanism at 30 K are 7 × 10{sup −16} cm{sup 3}/s for CN{sup −}, 7 × 10{sup −17} cm{sup 3}/s for C{sub 2}H{sup −}, and 2 × 10{sup −16} cm{sup 3}/s for C{sub 4}H{sup −}. These rates weakly depend on temperature between 10 K and 100 K. The validity of our calculations is verified by comparing the present theoretical results with data from recent photodetachment experiments.

  10. Equation of motion coupled cluster methods for electron attachment and ionization potential in fullerenes C60 and C70

    SciTech Connect

    Bhaskaran-Nair, Kiran; Kowalski, Karol; Moreno, Juana; Jarrell, Mark; Shelton, William A.

    2014-08-21

    Discovery of fullerenes has opened a entirely new chapter in chemistry due to their wide range of properties which holds exciting applications in numerous disciplines of science. The Nobel Prize in Chemistry 1996 was awarded jointly to Robert F. Curl Jr., Sir Harold W. Kroto and Richard E. Smalley in recoginition for their discovery of this new carbon allotrope. In this letter we are reporting ionization potential and electron attachment studies on fullerenes (C60 and C70) obtained with novel parallel implementation of the EA-EOM-CCSD and IP-EOM-CCSD methods in NWChem program package.

  11. Periodicity in Attachment Organelle Revealed by Electron Cryotomography Suggests Conformational Changes in Gliding Mechanism of Mycoplasma pneumoniae

    PubMed Central

    Kawamoto, Akihiro; Matsuo, Lisa; Kato, Takayuki; Yamamoto, Hiroki

    2016-01-01

    ABSTRACT Mycoplasma pneumoniae, a pathogenic bacterium, glides on host surfaces using a unique mechanism. It forms an attachment organelle at a cell pole as a protrusion comprised of knoblike surface structures and an internal core. Here, we analyzed the three-dimensional structure of the organelle in detail by electron cryotomography. On the surface, knoblike particles formed a two-dimensional array, albeit with limited regularity. Analyses using a nonbinding mutant and an antibody showed that the knoblike particles correspond to a naplike structure that has been observed by negative-staining electron microscopy and is likely to be formed as a complex of P1 adhesin, the key protein for binding and gliding. The paired thin and thick plates feature a rigid hexagonal lattice and striations with highly variable repeat distances, respectively. The combination of variable and invariant structures in the internal core and the P1 adhesin array on the surface suggest a model in which axial extension and compression of the thick plate along a rigid thin plate is coupled with attachment to and detachment from the substrate during gliding. PMID:27073090

  12. Modulation instability and dissipative rogue waves in ion-beam plasma: Roles of ionization, recombination, and electron attachment

    SciTech Connect

    Guo, Shimin Mei, Liquan

    2014-11-15

    The amplitude modulation of ion-acoustic waves is investigated in an unmagnetized plasma containing positive ions, negative ions, and electrons obeying a kappa-type distribution that is penetrated by a positive ion beam. By considering dissipative mechanisms, including ionization, negative-positive ion recombination, and electron attachment, we introduce a comprehensive model for the plasma with the effects of sources and sinks. Via reductive perturbation theory, the modified nonlinear Schrödinger equation with a dissipative term is derived to govern the dynamics of the modulated waves. The effect of the plasma parameters on the modulation instability criterion for the modified nonlinear Schrödinger equation is numerically investigated in detail. Within the unstable region, first- and second-order dissipative ion-acoustic rogue waves are present. The effect of the plasma parameters on the characteristics of the dissipative rogue waves is also discussed.

  13. Low energy (0-4 eV) electron impact to N{sub 2}O clusters: Dissociative electron attachment, ion-molecule reactions, and vibrational Feshbach resonances

    SciTech Connect

    Vizcaino, Violaine; Denifl, Stephan; Maerk, Tilmann D.; Scheier, Paul; Illenberger, Eugen

    2010-10-21

    Electron attachment to clusters of N{sub 2}O in the energy range of 0-4 eV yields the ionic complexes [(N{sub 2}O){sub n}O]{sup -}, [(N{sub 2}O){sub n}NO]{sup -}, and (N{sub 2}O){sub n}{sup -} . The shape of the ion yields of the three homologous series differs substantially reflecting the different formation mechanisms. While the generation of [(N{sub 2}O){sub n}O]{sup -} can be assigned to dissociative electron attachment (DEA) of an individual N{sub 2}O molecule in the target cluster, the formation of [(N{sub 2}O){sub n}NO]{sup -} is interpreted via a sequence of ion molecule reactions involving the formation of O{sup -} via DEA in the first step. The nondecomposed complexes (N{sub 2}O){sub n}{sup -} are preferentially formed at very low energies (below 0.5 eV) as a result of intramolecular stabilization of a diffuse molecular anion at low energy. The ion yields of [(N{sub 2}O){sub n}O]{sup -} and (N{sub 2}O){sub n}{sup -} versus electron energy show sharp peaks at the threshold region, which can be assigned to vibrational Feshbach resonances mediated by the diffuse anion state as already observed in an ultrahigh resolution electron attachment study of N{sub 2}O clusters [E. Leber, S. Barsotti, J. Boemmels, J. M. Weber, I. I. Fabrikant, M.-W. Ruf, and H. Hotop, Chem. Phys. Lett. 325, 345 (2000)].

  14. Comparative electron paramagnetic resonance investigation of reduced graphene oxide and carbon nanotubes with different chemical functionalities for quantum dot attachment

    SciTech Connect

    Pham, Chuyen V.; Krueger, Michael E-mail: emre.erdem@physchem.uni-freiburg.de; Eck, Michael; Weber, Stefan; Erdem, Emre E-mail: emre.erdem@physchem.uni-freiburg.de

    2014-03-31

    Electron paramagnetic resonance (EPR) spectroscopy has been applied to different chemically treated reduced graphene oxide (rGO) and multiwalled carbon nanotubes (CNTs). A narrow EPR signal is visible at g = 2.0029 in both GO and CNT-Oxide from carbon-related dangling bonds. EPR signals became broader and of lower intensity after oxygen-containing functionalities were reduced and partially transformed into thiol groups to obtain thiol-functionalized reduced GO (TrGO) and thiol-functionalized CNT (CNT-SH), respectively. Additionally, EPR investigation of CdSe quantum dot-TrGO hybrid material reveals complete quenching of the TrGO EPR signal due to direct chemical attachment and electronic coupling. Our work confirms that EPR is a suitable tool to detect spin density changes in different functionalized nanocarbon materials and can contribute to improved understanding of electronic coupling effects in nanocarbon-nanoparticle hybrid nano-composites promising for various electronic and optoelectronic applications.

  15. Experimental SF6/-//SF6 and Cl/-//CFC13 electron-attachment cross sections in the energy range 0-200 meV

    NASA Technical Reports Server (NTRS)

    Chutjian, A.

    1981-01-01

    Experimental cross sections for the electron-attachment processes for SF6(-)/SF6 and Cl(-)/CFl3 are reported in the energy range 0-200 meV by normalizing each attachment line shape to measurement of a thermal rate coefficient. When the same ion states are detected, good agreement is found between present values, for which a monoenergetic electron source is used, and swarm-unfolded results. The present data constitute a new limit for cross sections reported at high resolution at the lowest electron energy.

  16. Plane wave density functional theory studies of the structural and the electronic properties of amino acids attached to graphene oxide via peptide bonding

    NASA Astrophysics Data System (ADS)

    Min, Byeong June; Jeong, Hae Kyung; Lee, ChangWoo

    2015-08-01

    We studied via plane wave pseudopotential total-energy calculations within the local spin density approximation (LSDA) the electronic and the structural properties of amino acids (alanine, glycine, and histidine) attached to graphene oxide (GO) by peptide bonding. The HOMO-LUMO gap, the Hirshfeld charges, and the equilibrium geometrical structures exhibit distinctive variations that depend on the species of the attached amino acid. The GO-amino acid system appears to be a good candidate for a biosensor.

  17. Equation of motion coupled cluster methods for electron attachment and ionization potential in polyacenes

    SciTech Connect

    Bhaskaran-Nair, Kiran; Kowalski, Karol; Jarrell, Mark; Moreno, Juana; Shelton, William A.

    2015-11-05

    Polyacenes have attracted considerable attention due to their use in organic based optoelectronic materials. Polyacenes are polycyclic aromatic hydrocarbons composed of fused benzene rings. Key to understanding and design of new functional materials is an understanding of their excited state properties starting with their electron affinity (EA) and ionization potential (IP). We have developed a highly accurate and com- putationally e*fficient EA/IP equation of motion coupled cluster singles and doubles (EA/IP-EOMCCSD) method that is capable of treating large systems and large basis set. In this study we employ the EA/IP-EOMCCSD method to calculate the electron affinity and ionization potential of naphthalene, anthracene, tetracene, pentacene, hex- acene and heptacene. We have compared our results with other previous theoretical studies and experimental data. Our EA/IP results are in very good agreement with experiment and when compared with the other theoretical investigations our results represent the most accurate calculations as compared to experiment.

  18. Metastable anions of polyynes: Dynamics of fragmentation/stabilization in planetary atmospheres after electron attachment

    NASA Astrophysics Data System (ADS)

    Sebastianelli, F.; Gianturco, F. A.

    2012-02-01

    The quantum dynamics of low-energy free electrons colliding with linear carbonaceous species like HC3N and HC5N is examined to identify the locations and structural features of their metastable negative ions (resonant compound states of the colliding partners) with the aim of suggesting, at the molecular level, the possible mechanisms of anionic stabilization which lead to the several stable species observed in the interstellar and circumstellar media in connection with polyyne structures.

  19. Pressure dependence of critical temperature of bulk FeSe from spin fluctuation theory

    NASA Astrophysics Data System (ADS)

    Hirschfeld, Peter; Kreisel, Andreas; Wang, Yan; Tomic, Milan; Jeschke, Harald; Jacko, Anthony; Valenti, Roser; Maier, Thomas; Scalapino, Douglas

    2013-03-01

    The critical temperature of the 8K superconductor FeSe is extremely sensitive to pressure, rising to a maximum of 40K at about 10GPa. We test the ability of the current generation of fluctuation exchange pairing theories to account for this effect, by downfolding the density functional theory electronic structure for each pressure to a tight binding model. The Fermi surface found in such a procedure is then used with fixed Hubbard parameters to determine the pairing strength using the random phase approximation for the spin singlet pairing vertex. We find that the evolution of the Fermi surface captured by such an approach is alone not sufficient to explain the observed pressure dependence, and discuss alternative approaches. PJH, YW, AK were supported by DOE DE-FG02-05ER46236, the financial support of MT, HJ, and RV from the DFG Schwerpunktprogramm 1458 is kindly acknowledged.

  20. Neutron depolarization imaging of the hydrostatic pressure dependence of inhomogeneous ferromagnets

    NASA Astrophysics Data System (ADS)

    Schulz, M.; Neubauer, A.; Böni, P.; Pfleiderer, C.

    2016-05-01

    The investigation of fragile and potentially inhomogeneous forms of ferromagnetic order under extreme conditions, such as low temperatures and high pressures, is of central interest for areas such as geophysics, correlated electron systems, as well as the optimization of materials synthesis for applications where particular material properties are required. We report neutron depolarization imaging measurements on the weak ferromagnet Ni3Al under pressures up to 10 kbar using a Cu:Be clamp cell. Using a polychromatic neutron beam with wavelengths λ ≥ 4 Å in combination with 3He neutron spin filter cells as polarizer and analyzer, we were able to track differences of the pressure response in inhomogeneous samples by virtue of high resolution neutron depolarization imaging. This provides spatially resolved and non-destructive access to the pressure dependence of the magnetic properties of inhomogeneous ferromagnetic materials.

  1. Equation of motion coupled cluster methods for electron attachment and ionization potential in polyacenes

    NASA Astrophysics Data System (ADS)

    Bhaskaran-Nair, Kiran; Kowalski, Karol; Jarrell, Mark; Moreno, Juana; Shelton, William A.

    2015-11-01

    Polyacenes have attracted considerable attention due to their various applications in organic optoelectronic materials. This study focuses on linear polyacenes and their electron affinity (EA) and ionization potential (IP) properties. We have employed our recent implementation of EA/IP equation of motion coupled cluster singles and doubles (EA/IP-EOMCCSD) methods which are accurate, computationally efficient and are capable of treating large systems employing reasonable basis sets size. The EA/IP results obtained for naphthalene, anthracene, tetracene, pentacene, hexacene and heptacene are in a good agreement with experiment. Comparison between quality of excitation energies obtained from IP-EOMCCSD and EE-EOMCCSD formalisms were also studied.

  2. Remote electronic control of DNA hybridization through inductive coupling to an attached metal nanocrystal antenna

    NASA Astrophysics Data System (ADS)

    Hamad-Schifferli, Kimberly; Schwartz, John J.; Santos, Aaron T.; Zhang, Shuguang; Jacobson, Joseph M.

    2002-01-01

    Increasingly detailed structural and dynamic studies are highlighting the precision with which biomolecules execute often complex tasks at the molecular scale. The efficiency and versatility of these processes have inspired many attempts to mimic or harness them. To date, biomolecules have been used to perform computational operations and actuation, to construct artificial transcriptional loops that behave like simple circuit elements and to direct the assembly of nanocrystals. Further development of these approaches requires new tools for the physical and chemical manipulation of biological systems. Biomolecular activity has been triggered optically through the use of chromophores, but direct electronic control over biomolecular `machinery' in a specific and fully reversible manner has not yet been achieved. Here we demonstrate remote electronic control over the hybridization behaviour of DNA molecules, by inductive coupling of a radio-frequency magnetic field to a metal nanocrystal covalently linked to DNA. Inductive coupling to the nanocrystal increases the local temperature of the bound DNA, thereby inducing denaturation while leaving surrounding molecules relatively unaffected. Moreover, because dissolved biomolecules dissipate heat in less than 50picoseconds (ref. 16), the switching is fully reversible. Inductive heating of macroscopic samples is widely used, but the present approach should allow extension of this concept to the control of hybridization and thus of a broad range of biological functions on the molecular scale.

  3. Development of a Pressure-Dependent Constitutive Model with Combined Multilinear Kinematic and Isotropic Hardening

    NASA Technical Reports Server (NTRS)

    Allen Phillip A.; Wilson, Christopher D.

    2003-01-01

    The development of a pressure-dependent constitutive model with combined multilinear kinematic and isotropic hardening is presented. The constitutive model is developed using the ABAQUS user material subroutine (UMAT). First the pressure-dependent plasticity model is derived. Following this, the combined bilinear and combined multilinear hardening equations are developed for von Mises plasticity theory. The hardening rule equations are then modified to include pressure dependency. The method for implementing the new constitutive model into ABAQUS is given.

  4. Formation of aminyl radicals on electron attachment to AZT: Abstraction from the sugar phosphate backbone vs. one-electron oxidation of Guanine

    PubMed Central

    Adhikary, Amitava; Khanduri, Deepti; Pottiboyina, Venkata; Rice, Cory T.; Sevilla, Michael D.

    2010-01-01

    Employing electron spin resonance (ESR) spectroscopy, we have characterized the radicals formed in 3′-Azido-3′-deoxythymidine (3′-AZT) and in its 5′-analog 5′-azido-5′-deoxythymidine (5′-AZT) after electron attachment in γ-irradiated aqueous (H2O or D2O) glassy (7.5 M LiCl) systems. ESR spectral studies and theoretical calculations show that the predominant site of electron capture in 3′-AZT and in 5′-AZT is at the azide group and not at the thymine moiety. The azide group in AZT is therefore more electron affinic than the most electron affinic DNA base, thymine. Electron attachment to 3′-AZT and 5′-AZT results in an unstable azide anion radical intermediate (RN3•−) that is too short lived to be observed in our work even at 77 K. At 77 K we observe the neutral aminyl radical (RNH•) after loss of N2 from RN3•− followed by protonation of nitrene anion radical (RN•−) to give RNH•. The expected RN•− intermediate is not observed as protonation from water is complete at 77 K even in under highly basic conditions. Formation of RND• in D2O solutions confirms water as the source of the NH proton in the RNH•. Our assignments to these radicals are aided by DFT calculations for hyperfine coupling constants which closely match the experimental values. On annealing to higher temperatures (ca. 160–170 K), RNH• undergoes bimolecular hydrogen abstraction reactions from the thymine methyl group and the sugar moiety resulting in the formation of the thymine allyl radical (UCH2•) and two sugar radicals - C3′•, C5′•. RNH• also results in one-electron oxidation of the guanine base in 3′-AZG. This work provides a potential mechanism for the reported radiosensitization effects of AZT. PMID:20575557

  5. Electron attachment to CF3 and CF3Br at temperatures up to 890 K: Experimental test of the kinetic modeling approach

    NASA Astrophysics Data System (ADS)

    Shuman, Nicholas S.; Miller, Thomas M.; Viggiano, Albert A.; Troe, Jürgen

    2013-05-01

    Thermal rate constants and product branching fractions for electron attachment to CF3Br and the CF3 radical have been measured over the temperature range 300-890 K, the upper limit being restricted by thermal decomposition of CF3Br. Both measurements were made in Flowing Afterglow Langmuir Probe apparatuses; the CF3Br measurement was made using standard techniques, and the CF3 measurement using the Variable Electron and Neutral Density Attachment Mass Spectrometry technique. Attachment to CF3Br proceeds exclusively by the dissociative channel yielding Br-, with a rate constant increasing from 1.1 × 10-8 cm3 s-1 at 300 K to 5.3 × 10-8 cm3 s-1 at 890 K, somewhat lower than previous data at temperatures up to 777 K. CF3 attachment proceeds through competition between associative attachment yielding CF3- and dissociative attachment yielding F-. Prior data up to 600 K showed the rate constant monotonically increasing, with the partial rate constant of the dissociative channel following Arrhenius behavior; however, extrapolation of the data using a recently proposed kinetic modeling approach predicted the rate constant to turn over at higher temperatures, despite being only ˜5% of the collision rate. The current data agree well with the previous kinetic modeling extrapolation, providing a demonstration of the predictive capabilities of the approach.

  6. Electron attachment to CF3 and CF3Br at temperatures up to 890 K: experimental test of the kinetic modeling approach.

    PubMed

    Shuman, Nicholas S; Miller, Thomas M; Viggiano, Albert A; Troe, Jürgen

    2013-05-28

    Thermal rate constants and product branching fractions for electron attachment to CF3Br and the CF3 radical have been measured over the temperature range 300-890 K, the upper limit being restricted by thermal decomposition of CF3Br. Both measurements were made in Flowing Afterglow Langmuir Probe apparatuses; the CF3Br measurement was made using standard techniques, and the CF3 measurement using the Variable Electron and Neutral Density Attachment Mass Spectrometry technique. Attachment to CF3Br proceeds exclusively by the dissociative channel yielding Br(-), with a rate constant increasing from 1.1 × 10(-8) cm(3) s(-1) at 300 K to 5.3 × 10(-8) cm(3) s(-1) at 890 K, somewhat lower than previous data at temperatures up to 777 K. CF3 attachment proceeds through competition between associative attachment yielding CF3 (-) and dissociative attachment yielding F(-). Prior data up to 600 K showed the rate constant monotonically increasing, with the partial rate constant of the dissociative channel following Arrhenius behavior; however, extrapolation of the data using a recently proposed kinetic modeling approach predicted the rate constant to turn over at higher temperatures, despite being only ~5% of the collision rate. The current data agree well with the previous kinetic modeling extrapolation, providing a demonstration of the predictive capabilities of the approach. PMID:23742484

  7. Formation of negative ions in the interstellar medium by dissociative electron attachment to the H2CN molecule

    NASA Astrophysics Data System (ADS)

    Kokoouline, Viatcheslav; Fonseca Dos Santos, Samantha; Douguet, Nicolas; Orel, Ann

    2013-05-01

    The methylene amidogen radical (H2CN) was first discovered, in 1962 by Cochran et al ., and since then it has received considerable attention from both experimentalists and theoreticians. It is considered an important intermediate in the combustion of nitramine propellants and proposed to play a role in extraterrestrial atmospheres. It was detected in interstellar clouds in 1994, and its dissociative electron attachment (DEA) process may be responsible for the formation of the CN- and the H- negative ions: e-+H2CN --> CN- + H2; e-+H2CN --> H- + HCN. We report here the results of our ab initio quantum chemical studies of the geometrical and electronic structure of the methylene amidogen and and its negative ion H2CN- in the theoretical of DEA in H2CN. The scattering calculations are carried out using the complex Kohn variational method. The nuclear dynamics, including dissociation, will later be treated using the MCTDH code with a three-dimensional potential energy surface, in which the distance of CN is kept frozen. This work is supported by the DOE Office of Basic Energy Science and the National Science Foundation, Grant No's PHY-11-60611 and PHY-10-68785.

  8. Electron Paramagnetic Resonance of a Single NV Nanodiamond Attached to an Individual Biomolecule.

    PubMed

    Teeling-Smith, Richelle M; Jung, Young Woo; Scozzaro, Nicolas; Cardellino, Jeremy; Rampersaud, Isaac; North, Justin A; Šimon, Marek; Bhallamudi, Vidya P; Rampersaud, Arfaan; Johnston-Halperin, Ezekiel; Poirier, Michael G; Hammel, P Chris

    2016-05-10

    Electron paramagnetic resonance (EPR), an established and powerful methodology for studying atomic-scale biomolecular structure and dynamics, typically requires in excess of 10(12) labeled biomolecules. Single-molecule measurements provide improved insights into heterogeneous behaviors that can be masked in ensemble measurements and are often essential for illuminating the molecular mechanisms behind the function of a biomolecule. Here, we report EPR measurements of a single labeled biomolecule. We selectively label an individual double-stranded DNA molecule with a single nanodiamond containing nitrogen-vacancy centers, and optically detect the paramagnetic resonance of nitrogen-vacancy spins in the nanodiamond probe. Analysis of the spectrum reveals that the nanodiamond probe has complete rotational freedom and that the characteristic timescale for reorientation of the nanodiamond probe is slow compared with the transverse spin relaxation time. This demonstration of EPR spectroscopy of a single nanodiamond-labeled DNA provides the foundation for the development of single-molecule magnetic resonance studies of complex biomolecular systems. PMID:27166812

  9. Time-resolved radiation chemistry: Dynamics of electron attachment to uracil following UV excitation of iodide-uracil complexes

    SciTech Connect

    King, Sarah B.; Yandell, Margaret A.; Stephansen, Anne B.; Neumark, Daniel M.

    2014-12-14

    Electron attachment to uracil was investigated by applying time-resolved photoelectron imaging to iodide-uracil (I{sup –}U) complexes. In these studies, an ultraviolet pump pulse initiated charge transfer from the iodide to the uracil, and the resulting dynamics of the uracil temporary negative ion were probed. Five different excitation energies were used, 4.00 eV, 4.07 eV, 4.14 eV, 4.21 eV, and 4.66 eV. At the four lowest excitation energies, which lie near the vertical detachment energy of the I{sup –}U complex (4.11 eV), signatures of both the dipole bound (DB) as well as the valence bound (VB) anion of uracil were observed. In contrast, only the VB anion was observed at 4.66 eV, in agreement with previous experiments in this higher energy range. The early-time dynamics of both states were highly excitation energy dependent. The rise time of the DB anion signal was ∼250 fs at 4.00 eV and 4.07 eV, ∼120 fs at 4.14 eV and cross-correlation limited at 4.21 eV. The VB anion rise time also changed with excitation energy, ranging from 200 to 300 fs for excitation energies 4.00–4.21 eV, to a cross-correlation limited time at 4.66 eV. The results suggest that the DB state acts as a “doorway” state to the VB anion at 4.00–4.21 eV, while direct attachment to the VB anion occurs at 4.66 eV.

  10. Pressure dependence of Se absorption lines in AlSb

    SciTech Connect

    Hsu, L. |; Haller, E.E.; Ramdas, A.K.

    1996-09-01

    Using far infrared absorption spectroscopy, the authors have investigated electronic transition spectra of Se donors in AlSb as a function of hydrostatic pressure. At least two distinct ground to bound excited state transition lines, which depend quadratically on the pressure, can be seen. At pressures between 30 and 50 kbar, evidence of an anti-crossing between one of the electronic transitions and a peak which they attribute to the 2 zone center LO phonon mode can be seen.

  11. Electron Attachment in Low-Energy Electron Elastic Collisions with Au and Pt Atoms: Identification of Excited Anions

    NASA Astrophysics Data System (ADS)

    Msezane, A. Z.; Eure, A.; Felfli, Z.; Sokolovski, D.

    2009-11-01

    The recent Regge-pole methodology has been benchmarked [1] on the accurately measured binding energies of the excited Ge= and Sn= anions [2] through the binding energies (BEs) extracted from the Regge-pole calculated elastic total cross sections (TCSs). Here the methodology is applied together with a Thomas-Fermi type potential that incorporates the vital core polarization interaction to investigate the possibility of forming excited Au= and Pt= anions in low-energy electron elastic collisions with Au and Pt atoms. From the positions of the characteristic extremely narrow resonances in the total cross sections, we extract the binding energies of the excited Au= and Pt= anions formed as Regge resonances during the collisions. The angular life of the complexes thus formed is used to differentiate the stable excited bound states of the anions from the shape resonances [3]. The BEs for the excited Au= and Pt= anions are found to be 0.475eVand 0.543eV, respectively, challenging both theory and experiment to verify. [1] A. Msezane et al, Phys. Rev. A, Submitted (2009) [2] M. Scheer et al, Phys. Rev. A 58, 2844 (1998) [3] Z. Felfli et al, Phys. Rev. A 79, 012714 (2009)

  12. The wavelength dependence of photoinduced hot electron dissociative attachment to methyl bromide adsorbed on gallium arsenide (110)

    SciTech Connect

    Camillone, N. III; Khan, K.A.; Lasky, P.J.; Wu, L.; Moryl, J.E.; Osgood, R.M. Jr.

    1998-11-01

    The wavelength dependence of photoinduced dissociation of CH{sub 3}Br via dissociative electron attachment (DEA) of {open_quotes}hot{close_quotes} electrons for one monolayer CH{sub 3}Br adsorbed on GaAs(110) has been measured. The cross section for dissociation is found to decrease monotonically by two orders of magnitude as the incident wavelength is varied from 308 to 550 nm. There is an apparent threshold near 490 nm (2.5 eV), well below the gas phase photodissociation threshold near 250 nm (5.0 eV), but in good agreement with a simple estimate based on expected values for the decrease in the photoemission threshold and the lowering of the molecular affinity level upon adsorption of CH{sub 3}Br on a semiconductor surface. The observed threshold is found to move to higher energy as dissociation of the monolayer proceeds. Based on the work of Hasselbrink and co-workers [F. Weik, A. de Meijere, and E. Hasselbrink, J. Chem. Phys. {bold 99}, 682 (1993)], a simple theoretical model is developed which considers the tunneling of hot electrons through the interfacial barrier between the physisorbed CH{sub 3}Br and the GaAs. The results of our theoretical model in conjunction with those of earlier {ital ab initio} calculations [S. Black, R. Friesner, P. H. Lu, and R. M. Osgood, Jr., Surf. Sci. {bold 382}, 154 (1997)] suggest that the adsorbate affinity level is centered at {approximately}0.6 eV above the (adsorbate- modified) vacuum level of the substrate. This value corresponds to a {approximately}1.8 eV stabilization of the negative ion resonance upon adsorption. {copyright} {ital 1998 American Institute of Physics.}

  13. Pressure dependence of donor excitation spectra in AlSb

    SciTech Connect

    Hsu, L.; McCluskey, M.D.; Haller, E.E.

    2002-01-16

    We have investigated the behavior of ground to bound excited-state electronic transitions of Se and Te donors in AlSb as a function of hydrostatic pressure. Using broadband far-infrared Fourier transform spectroscopy, we observe qualitatively different behaviors of the electronic transition energies of the two donors. While the pressure derivative of the Te transition energy is small and constant, as might be expected for a shallow donor, the pressure derivatives of the Se transition energies are quadratic and large at low pressures, indicating that Se is actually a deep donor. In addition, at pressures between 30 and 50 kbar, we observe evidence of an anti-crossing between one of the selenium electronic transitions and a two-phonon mode.

  14. Pressure dependent resistivity and magnetic measurements on superconducting KFe2As2

    NASA Astrophysics Data System (ADS)

    Kaluarachchi, Udhara; Taufour, Valentin; Tanatar, Makariy A.; Kim, Stella K.; Liu, Yong; Lograsso, Thomas A.; Bud'Ko, Sergey L.; Canfield, Paul C.; Foroozani, Neda; Lim, Jinhyuk; Schilling, James S.

    2014-03-01

    Ba1-xKxFe2As2 shows superconductivity at Tc ~ 38 K at the optimal doping (x ~ 0 . 4). However, superconductivity is still observed up to the extreme hole doping (x = 1) in KFe2As2 with a reduced Tc ~ 3 . 4 K. At this extreme limit, there is no observed electron pocket in this compound. The superconducting state is believed to be of a different symmetry than in the other 122 iron based superconductors. By means of resistivity, magnetization and AC susceptibility under pressure, we investigate the properties of this material. The pressure dependence of Tc has a change of slope around 2 GPa possibly consistent with a transition to a superconducting state of a different symmetry [F. F. Tafti, et al., Nature Physics 9, 349 (2013)]. We will compare measurements performed in different pressure media and discuss the evolution of the electronic correlations with applied pressure. Work at Ames Laboratory supported by AFOSR-MURI grant FA9550-09-1-0603 and by US DOE under the Contract No. DE-AC02-07CH11358. Work at Washington University supported by NSF Grant No. DMR-1104742 and by the Carnegie/DOE Alliance Center through NNSA/DOE Grant No. DE-FC52-08NA28554.

  15. Pressure dependence of the P/sub b/ center at the <111> Si/SiO/sub 2/ interface

    SciTech Connect

    Johnson, N.M.; Shan, W.; Yu, P.Y.

    1989-02-15

    We report the first measurement of the pressure dependence of the electronic gap states at the Si/SiO/sub 2/ interface that are associated with the paramagnetic defect termed the P/sub b/ center. The energy level of this amphoteric defect for the transition from double to single occupancy by holes is found by deep-level transient spectroscopy to shift towards the valence-band edge with increasing pressure. Our results are in agreement with the predictions of a cluster-model calculation in which the P/sub b/ center is identified with the dangling orbital of an interfacial threefold-coordinated Si atom.

  16. SURFACE FINISHES ON STAINLESS STEEL REDUCE BACTERIAL ATTACHMENT AND EARLY BIOFILM FORMATION: SCANNING ELECTRON AND ATOMIC FORCE MICROSCOPY STUDY

    EPA Science Inventory

    Three common finishing treatments of stainless steel that are used for equipment during poultry processing were tested for resistance to bacterial contamination. Methods were developed to measure attached bacteria and to identify factors that make surface finishes susceptible or ...

  17. Interesting pressure dependence of power factor in BiTeI

    NASA Astrophysics Data System (ADS)

    Guo, San-Dong; Wang, Jian-Li

    2016-06-01

    We investigate pressure dependence of electronic structures and thermoelectric properties in BiTeI by using a modified Becke and Johnson exchange potential. Spin–orbit coupling (SOC) effects are also included due to giant Rashba splitting. Thermoelectric properties are illuminated through solving Boltzmann transport equations within the constant scattering time approximation. The calculated energy band gap of 0.36 eV agrees well with the experimental value of 0.38 eV. As the pressure increases, the energy band gap first decreases, and then increases. The Rashba energy has the opposite trend with the energy band gap. SOC has obvious detrimental influence on the power factor in both n-type and p-type doping. For low doping concentration, the power factor has the same trend with the energy band gap with increasing pressure, but shows a monotonic changing trend in high doping. It is found that the pressure can induce a significantly enhanced power factor in high n-type doping, which can be understood as pressure leading to two-dimensional-like density of states in the conduction bands. These results suggest that BiTeI may be a potential candidate for efficient thermoelectricity in n-type doping by pressure, turning an ordinary insulator into a topological insulator.

  18. Pressure Dependence of Excitation Cross Sections for Resonant Levels of Rare Gases

    NASA Astrophysics Data System (ADS)

    Stewart, Michael D.; Chilton, J. Ethan; Lin, Chun C.

    2000-06-01

    In the rare gases, the excited n'p^5ns and n'p^5nd levels with J = 1 are optically coupled to ground as well as lower lying p levels. Resonant photons emitted when the atom decays to ground can be reabsorbed by another ground-state atom. At low gas pressures this reabsorption occurs infrequently, but at higher pressures becomes increasingly likely until the resonant transition is completely suppressed. This enhances the cascade transitions into lower p levels, resulting in pressure dependent optical emission cross sections. This reabsorption process can be understood quantitatively with a model developed by Heddle et al(D. W. O. Heddle and N. J. Samuel, J. Phys. B 3), 1593 (1970).. The radiation from transitions into the nonresonant levels often lie in the ir, while the resonant radiation is always in the uv spectral region. Using a Fourier-transform spectrometer, one can measure the cross sections for the ir transitions as a function of pressure. The Heddle model can be fit to these data with the use of theoretical values for the Einstein A coefficients. This provides a test of the accuracy of calculated A values. Discussion will include cross section measurements for Ne, Ar, and Kr excited by electron impact over a range of gas pressures.

  19. Calculation of SF6-/SF6 and Cl-/CFCl3 electron attachment cross sections in the energy range 0-100 meV

    NASA Technical Reports Server (NTRS)

    Chutjian, A.

    1982-01-01

    Electron attachment cross sections for the processes SF6-/SF6 and Cl-/CFCl3 are calculated in a local theory using a model in which diatomic-like potential energy curves for the normal modes are constructed from available spectroscopic data. Thermally populated vibrational and rotational levels are included. Good agreement is found with experimental cross sections in the energy range 5-100 meV for a particular choice of potential energy curve parameters.

  20. Attachment Disorganization.

    ERIC Educational Resources Information Center

    Solomon, Judith, Ed.; George, Carol, Ed.

    Disorganized attachment relationships were first formally identified on the basis of the anomalous behavior of some infants during laboratory separations and reunions with the parent. This book presents new research and theory on the topic of attachment disorganization, an area of investigation that is of increasing importance in the study of…

  1. 46 CFR 67.218 - Optional filing of instruments in portable document format as attachments to electronic mail.

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... mail (e-mail) for filing at the National Vessel Documentation Center. The e-mail address to be used for..., and submitted as an attachment to e-mail. (c) The e-mail required by paragraph (b) should indicate: (1) The name, address, telephone number, and e-mail address of the person submitting the instrument...

  2. 46 CFR 67.218 - Optional filing of instruments in portable document format as attachments to electronic mail.

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... mail (e-mail) for filing at the National Vessel Documentation Center. The e-mail address to be used for..., and submitted as an attachment to e-mail. (c) The e-mail required by paragraph (b) should indicate: (1) The name, address, telephone number, and e-mail address of the person submitting the instrument...

  3. 46 CFR 67.218 - Optional filing of instruments in portable document format as attachments to electronic mail.

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ... mail (e-mail) for filing at the National Vessel Documentation Center. The e-mail address to be used for..., and submitted as an attachment to e-mail. (c) The e-mail required by paragraph (b) should indicate: (1) The name, address, telephone number, and e-mail address of the person submitting the instrument...

  4. 46 CFR 67.218 - Optional filing of instruments in portable document format as attachments to electronic mail.

    Code of Federal Regulations, 2012 CFR

    2012-10-01

    ... mail (e-mail) for filing at the National Vessel Documentation Center. The e-mail address to be used for..., and submitted as an attachment to e-mail. (c) The e-mail required by paragraph (b) should indicate: (1) The name, address, telephone number, and e-mail address of the person submitting the instrument...

  5. A simple way to model the pressure dependency of rock velocity

    NASA Astrophysics Data System (ADS)

    Han, Tongcheng

    2016-04-01

    Modeling the pressure dependency of rock velocity is important for interpreting and comparing the seismic and earthquake data from different depths. This study develops a multicomponent differential effective medium model for the elastic properties of porous rocks with two types of pores in the grain background without mixing order. The developed model is applied to modeling the pressure dependent elastic velocity of porous rocks by incorporating the variation of stiff and compliant porosity as a function of pressure. The pressure dependent stiff and compliant porosity were inverted from the measured total porosity under pressure using a dual porosity model, and the unknown constant stiff and compliant pore aspect ratios were inverted by best fitting the modeled velocity to the measured data. Application of the approach to a low porosity granite and a medium porosity sandstone sample showed that the pressure dependency of rock velocity can be satisfactorily modeled by the developed model using the pressure dependent stiff and compliant porosity and carefully estimated stiff and compliant pore aspect ratio values.

  6. Electron attachment to C{sub 7}F{sub 14} and SF{sub 6} in a thermally ionized potassium plasma

    SciTech Connect

    Kim, Su-Hyun; Merlino, Robert L.

    2007-09-15

    Electron attachment to perfluoromethylcyclohexane (C{sub 7}F{sub 14}) and sulfur hexafluoride (SF{sub 6}) is studied in a Q machine which produces a thermally ionized potassium plasma at an electron temperature T{sub e}{approx_equal}0.2 eV (2300 K). Negative ion formation is observed by Langmuir probe measurements of the reduction in electron density as electrons attach to C{sub 7}F{sub 14} to form C{sub 7}F{sub 14}{sup -} or to SF{sub 6} to produce SF{sub 6}{sup -}. In C{sub 7}F{sub 14} at a pressure {approx}3x10{sup -5} Torr, a nearly electron-free plasma is formed with a residual electron-to-ion density ratio n{sub e}/n{sub +}<10{sup -4}. Formation of the C{sub 7}F{sub 14}{sup -} negative ion was confirmed by the presence of the C{sub 7}F{sub 14}{sup -} electrostatic ion cyclotron wave mode in the power spectrum of current-driven plasma oscillations. Measurements of the negative ion-to-electron density ratio, n{sub -}/n{sub e} for different pressures in both C{sub 7}F{sub 14} and SF{sub 6} indicate that for thermal electrons at 2300 K larger values of n{sub -}/n{sub e} are obtained in C{sub 7}F{sub 14} at a lower pressure than in SF{sub 6}.

  7. Calculation of rate constants for dissociative attachment of low-energy electrons to hydrogen halides HCl, HBr, and HI and their deuterated analogs

    SciTech Connect

    Houfek, Karel; Cizek, Martin; Horacek, Jiri

    2002-12-01

    Calculations of rate constants for the process of dissociative attachment of low-energy electrons to hydrogen halides HCl, HBr, and HI and for the reverse process of associative detachment based on the nonlocal resonance model are reported. The calculated data are of importance for the modeling of plasma processes, environmental chemistry, etc. The calculated dissociative attachment rate constants are found to be in good agreement with existing experimental data. It is shown that at low temperatures the rate constants are very sensitive to small changes of the parameters of the nonlocal resonance model used for the calculation of the rate constants and represent a severe test of the theory. The isotopic effect and its dependence on the temperature is also discussed. The calculations of rate constants for the reverse process of associative detachment are also reported and discussed.

  8. The effect of two different demineralization methods with saturated tetracycline hydrochloride on the attachment and growth of gingival fibroblasts. A scanning electron microscopic study.

    PubMed

    Babay, N; Mokeem, S

    2005-03-01

    The purpose of the present study was to evaluate in vitro, the influence of two different methods of surfaces conditioning of dentin by tetracycline hydrochloride on human gingival epithelial cell attachment. A flat dentin surface was created on human teeth extracted due to severe periodontitis: 36 specimens were divided into 3 equal groups and etched in the following way: group 1 (saline); group 2 (immersion in TTC for 3 min); group 3 (burnishing with TTC for 3 min). The specimens and fibroblasts were incubated in a culture medium for 24 hours, one and two weeks and photographed using scanning electron microscope. No fibroblasts could be seen on the saline groups. More fibroblasts could attach to the root surface at one and two weeks irrespective of the method used. PMID:16032945

  9. A pressure dependence model for the band gap energy of the dilute nitride GaNP

    NASA Astrophysics Data System (ADS)

    Zhao, Chuan-Zhen; Wei, Tong; Li, Na-Na; Wang, Sha-Sha; Lu, Ke-Qing

    2014-08-01

    The pressure dependence of the band gap energy of the dilute nitride GaNP is analyzed. It is found that the pressure dependence of the Г conduction band minimum (CBM) is stronger than that of the X CBM. We also find that the energy difference between the X CBM and the Г CBM in GaNP becomes large with increasing N content. In order to describe the pressure dependence of the band gap energy of the dilute nitride GaNP, a model is developed. Based on the model, we obtain the energy difference between the X CBM and the Г CBM in GaNP at standard atmospheric pressure. It agrees well with the results obtained by other method.

  10. Kinetic analysis of thymocyte attachment to thymus stromal cells in culture by using phase-contrast and scanning electron microscopy

    SciTech Connect

    LaRochelle, G.G.; Jones, K.H.

    1989-05-01

    Direct cellular contact between thymocytes and thymus stromal cells within the thymus appears to contribute to the maturation of thymocytes. Thymocyte-stromal cell complexes, formed in vivo, have been isolated by others and postulated to play a role in T-cell differentiation. These previous studies have been hampered, however, by a time-consuming isolation procedure from which only small numbers of these complexes are recovered. We have examined a model to study thymocyte-stromal cell complexes in vitro in which thymocytes are added to primary cultures of thymus stromal cells. In the present study, we found that thymocytes were histotypically selective in their attachment to thymus stromal cells. We also investigated the kinetics of thymocyte attachment to these thymus stromal cells. Cultures were examined at selected time intervals from 5 min through 3 days of incubation. Thymocyte attachment to stromal cells was a biphasic interaction, with maximum surface attachment at 15 min of cocultivation, followed by migration of thymocytes into the cultures. Morphological studies were confirmed by using /sup 3/H-leucine-labeled thymocytes and liquid scintigraphy. With increased time in culture, thymocytes became amoeboid and migrated between the layers of stromal cells where thymocyte mitotic figures were seen at 4 and 8 hr. In some cases it appeared that stromal cells, which often grew two to three cell layers deep, played an active role in enclosing thymocytes within the cultures. Large numbers of viable thymocytes were observed in the cultures at 24 hr. The number of thymocytes then decreased progressively on days 2 and 3, when relatively few were found within the layers of the culture.

  11. Spindly attachments

    PubMed Central

    Çivril, Filiz; Musacchio, Andrea

    2008-01-01

    The attachment of chromosomes to spindle microtubules during mitosis is a delicate and intricate process on which eukaryotic cells critically depend to maintain their ploidy. In this issue of Genes & Development, Gassmann and colleagues (pp. 2385–2399 present an analysis of the recently discovered Spindly/SPDL-1 protein that casts new lights onto the attachment process and the way it relates to the control of cell cycle progression. PMID:18765786

  12. Dissociative electron attachment to DNA-diamine thin films: Impact of the DNA close environment on the OH{sup −} and O{sup −} decay channels

    SciTech Connect

    Boulanouar, Omar; Fromm, Michel; Mavon, Christophe; Cloutier, Pierre; Sanche, Léon

    2013-08-07

    We measure the desorption of anions stimulated by the impact of 0–20 eV electrons on highly uniform thin films of plasmid DNA-diaminopropane. The results are accurately correlated with film thickness and composition by AFM and XPS measurements, respectively. Resonant structures in the H{sup −}, O{sup −}, and OH{sup −} yield functions are attributed to the decay of transient anions into the dissociative electron attachment (DEA) channel. The diamine induces ammonium-phosphate bridges along the DNA backbone, which suppresses the DEA O{sup −} channel and in counter-part increases considerably the desorption of OH{sup −}. The close environment of the phosphate groups may therefore play an important role in modulating the rate and type of DNA damages induced by low energy electrons.

  13. Dissociative electron attachment to DNA-diamine thin films: Impact of the DNA close environment on the OH- and O- decay channels

    NASA Astrophysics Data System (ADS)

    Boulanouar, Omar; Fromm, Michel; Mavon, Christophe; Cloutier, Pierre; Sanche, Léon

    2013-08-01

    We measure the desorption of anions stimulated by the impact of 0-20 eV electrons on highly uniform thin films of plasmid DNA-diaminopropane. The results are accurately correlated with film thickness and composition by AFM and XPS measurements, respectively. Resonant structures in the H-, O-, and OH- yield functions are attributed to the decay of transient anions into the dissociative electron attachment (DEA) channel. The diamine induces ammonium-phosphate bridges along the DNA backbone, which suppresses the DEA O- channel and in counter-part increases considerably the desorption of OH-. The close environment of the phosphate groups may therefore play an important role in modulating the rate and type of DNA damages induced by low energy electrons.

  14. Dissociative electron attachment to DNA-diamine thin films: Impact of the DNA close environment on the OH− and O− decay channels

    PubMed Central

    Boulanouar, Omar; Fromm, Michel; Mavon, Christophe; Cloutier, Pierre; Sanche, Léon

    2013-01-01

    We measure the desorption of anions stimulated by the impact of 0–20 eV electrons on highly uniform thin films of plasmid DNA-diaminopropane. The results are accurately correlated with film thickness and composition by AFM and XPS measurements, respectively. Resonant structures in the H−, O−, and OH− yield functions are attributed to the decay of transient anions into the dissociative electron attachment (DEA) channel. The diamine induces ammonium-phosphate bridges along the DNA backbone, which suppresses the DEA O− channel and in counter-part increases considerably the desorption of OH−. The close environment of the phosphate groups may therefore play an important role in modulating the rate and type of DNA damages induced by low energy electrons. PMID:23927286

  15. Electronic transport, transition-voltage spectroscopy, and the Fano effect in single molecule junctions composed of a biphenyl molecule attached to metallic and semiconducting carbon nanotube electrodes.

    PubMed

    Brito da Silva Júnior, Carlos Alberto; Leal, José Fernando Pereira; Aleixo, Vicente Ferrer Pureza; Pinheiro, Felipe A; Del Nero, Jordan

    2014-09-28

    We have investigated electronic transport in a single-molecule junction composed of a biphenyl molecule attached to a p-doped semiconductor and metallic carbon nanotube leads. We find that the current-voltage characteristics are asymmetric as a result of the different electronic natures of the right and left leads, which are metallic and semiconducting, respectively. We provide an analysis of transition voltage spectroscopy in such a system by means of both Fowler-Nordheim and Lauritsen-Millikan plots; this analysis allows one to identify the positions of resonances and the regions where the negative differential conductance occurs. We show that transmittance curves are well described by the Fano lineshape, for both direct and reverse bias, demonstrating that the frontier molecular orbitals are effectively involved in the transport process. This result gives support to the interpretation of transition voltage spectroscopy based on the coherent transport model. PMID:25109887

  16. Experimental and theoretical investigation of pressure-dependent Raman spectra of triaminotrinitrobenzene (TATB) at high pressures

    NASA Astrophysics Data System (ADS)

    Landerville, Aaron; Grant, Christian; Zaug, Joseph; Crowhurst, Jonathan; Oleynik, Ivan

    2015-06-01

    The experimental pressure dependent Raman spectra of triamino-trinitrobenzene (TATB) are determined up to 27 GPa, and compared with those obtained using density functional theory (DFT). The density functional perturbation theory calculations include the Grimme empirical van der Waals correction, as well as corrections for both thermal and zero-point energy contributions to pressure. DFT calculations of the crystal structure of TATB at ambient conditions, the equation of state, and Raman spectra up to 25 GPa are in good agreement with experiment. Pressure-dependence of specific vibrational modes is discussed in detail. Further, the comparison of experimental and calculated Raman spectra of TATB offers evidence that no first-order polymorphic phase transition occurs at least up to 25 GPa.

  17. Optical properties of silver nanocomposites and photonic band gap - Pressure dependence

    NASA Astrophysics Data System (ADS)

    Ramanujam, N. R.; Wilson, K. S. Joseph

    2016-06-01

    We theoretically investigate the effect of photonic band gaps in one dimensional photonic crystals based on nanocomposite of silver nanoparticles. The dielectric permittivity is computed based on the pressure dependence of plasma frequency and damping constant of silver nanoparticle. It leads to the tuning of photonic band gap. We have also investigated the change in photonic band gap due to the influence of filling factor and the size of the nanoparticles. Our results provide a guideline for designing potential photonic devices.

  18. Pressure dependence of the melting temperature of solids - Rare-gas solids

    NASA Technical Reports Server (NTRS)

    Schlosser, Herbert; Ferrante, John

    1991-01-01

    A method presented by Schlosser et al. (1989) for analyzing the pressure dependence of experimental melting-temperature data is applied to rare-gas solids. The plots of the logarithm of the reduced melting temperature vs that of the reduced pressure are straight lines in the absence of phase transitions. The plots of the reduced melting temperatures for Ar, Kr, and Xe are shown to be approximately straight lines.

  19. THE INFLUENCE OF PRESSURE-DEPENDENT VISCOSITY ON THE THERMAL EVOLUTION OF SUPER-EARTHS

    SciTech Connect

    Stamenkovic, Vlada; Noack, Lena; Spohn, Tilman; Breuer, Doris E-mail: Lena.Noack@dlr.de E-mail: Tilman.Spohn@dlr.de

    2012-03-20

    We study the thermal evolution of super-Earths with a one-dimensional (1D) parameterized convection model that has been adopted to account for a strong pressure dependence of the viscosity. A comparison with a 2D spherical convection model shows that the derived parameterization satisfactorily represents the main characteristics of the thermal evolution of massive rocky planets. We find that the pressure dependence of the viscosity strongly influences the thermal evolution of super-Earths-resulting in a highly sluggish convection regime in the lower mantles of those planets. Depending on the effective activation volume and for cooler initial conditions, we observe with growing planetary mass even the formation of a conductive lid above the core-mantle boundary (CMB), a so-called CMB-lid. For initially molten planets our results suggest no CMB-lids but instead a hot lower mantle and core as well as sluggish lower mantle convection. This implies that the initial interior temperatures, especially in the lower mantle, become crucial for the thermal evolution-the thermostat effect suggested to regulate the interior temperatures in terrestrial planets does not work for massive planets if the viscosity is strongly pressure dependent. The sluggish convection and the potential formation of the CMB-lid reduce the convective vigor throughout the mantle, thereby affecting convective stresses, lithospheric thicknesses, and heat fluxes. The pressure dependence of the viscosity may therefore also strongly affect the propensity of plate tectonics, volcanic activity, and the generation of a magnetic field of super-Earths.

  20. First-principles characterisation of the pressure-dependent elastic anisotropy of SnO2 polymorphs

    NASA Astrophysics Data System (ADS)

    Das, Pratik Kumar; Chowdhury, Anjan; Mandal, Nibir; Arya, A.

    2016-06-01

    Using DFT calculations, this study investigates the pressure-dependent variations of elastic anisotropy in the following SnO2 phases: rutile-type (tetragonal; P42/mnm), CaCl2-type (orthorhombic; Pnnm)-, α-PbO2-type (orthorhombic; Pbcn)- and fluorite-type (cubic; Fm-3m). Experimentally, these polymorphs undergo sequential structural transitions from rutile-type → CaCl2-type → α-PbO2-type → fluorite-type with increasing pressure at 11.35, 14.69 and 58.22 GPa, respectively. We estimate the shear anisotropy (A1 and A3) on {1 0 0} and {0 0 1} crystallographic planes of the tetragonal phase and (A1, A2 and A3) on {1 0 0}, {0 1 0} and {0 0 1} crystallographic planes of the orthorhombic phases. The rutile-type phase shows strongest shear anisotropy on the {0 0 1} planes (A2 > 4.8), and the degree of anisotropy increases nonlinearly with pressure. In contrast, the anisotropy is almost absent on the {1 0 0} planes (ie A1 1) irrespective of the pressure. The CaCl2-type phase exhibits similar shear anisotropy behaviour preferentially on {0 0 1} (A3 > 5), while A1 and A2 remain close to 1. The α-PbO2-type phase shows strikingly different elastic anisotropy characterised by a reversal in anisotropy (A3 > 1 to < 1) with increasing pressure at a threshold value of 38 GPa. We provide electronic density of states and atomic configuration to account for this pressure-dependent reversal in shear anisotropy. Our study also analyses the directional Young's moduli for the tetragonal and orthorhombic phases as a function of pressure. Finally, we estimate the band gaps of these four SnO2 phases as a function of pressure which are in agreement with the previous results.

  1. Electron attachment line shapes, cross sections, and rate constants at ultralow energies in CF3SO3H, (CF3SO2)2O, and CF3I

    NASA Technical Reports Server (NTRS)

    Alajajian, S. H.; Man, K.-F.; Chutjian, A.

    1991-01-01

    Electron attachment cross sections are reported in the energy range 0-160 meV, and at resolutions of 6.0-6.5 meV (FWHM) for the molecules CF3SO3H (triflic acid), (CF3SO2)2O (triflic anhydride), and CF3I (methyl iodide). Use is made of the Kr photoionization method. Attachment line shapes are deconvoluted from the spectral slit (electron energy) function, and are converted to cross sections by normalization to thermal attachment rate constants at 300 K. Rate constants as a function of mean electron energy are calculated from the cross sections using a Maxwellian electron energy distribution function. Present data are compared with flowing-afterglow, Langmuir-probe results in triflic acid and anhydride, and with high-Rydberg ionization results in CF3I.

  2. Dissociative electron attachment to CH2Cl2, CHCH3Cl2, and C(CH3)2Cl2

    NASA Astrophysics Data System (ADS)

    Gallup, Gordon A.; Fabrikant, Ilya I.

    2011-10-01

    We perform theoretical studies of dissociative electron attachment (DEA) for the compounds CH2 - n(CH3)nCl2, n = 0, 1, 2, by combining the finite-element discrete model with the resonance R-matrix theory. An unexpectedly low DEA cross section for CH2Cl2 is likely due to the relatively large resonance width for this compound that confirms experimental observations. However, there are some quantitative discrepancies with the experimental results. Since DEA cross sections are very sensitive to the resonance width, a slight adjustment of its value can significantly improve agreement between theory and experiment. Our calculation of the thermal rate coefficients show that there are some inconsistencies between beam and swarm measurements and between different swarm measurements of the rate coefficients for DEA to CH2Cl2. Further experimental and theoretical studies are warranted.

  3. Effects of temperature and isotopic substitution on electron attachment dynamics of guanine-cytosine base pair: Ring-polymer and classical molecular dynamics simulations

    NASA Astrophysics Data System (ADS)

    Minoshima, Yusuke; Seki, Yusuke; Takayanagi, Toshiyuki; Shiga, Motoyuki

    2016-06-01

    The dynamical process of electron attachment to a guanine-cytosine pair in the normal (h-GC) and deuterated (d-GC) forms has been studied theoretically by semiclassical ring-polymer molecular dynamics (RPMD) simulations using the empirical valence bond model. The initially formed dipole-bound anion is converted rapidly to the valence-bound anion within about 0.1 ps in both h-GC and d-GC. However, the subsequent proton transfer in h-GC occurs with a rate five times greater than the deuteron transfer in d-GC. The change of rates with isotopic substitution and temperature variation in the RPMD simulations are quantitatively and qualitatively different from those in the classical molecular dynamics (MD) simulations, demonstrating the importance of nuclear quantum effects on the dynamics of this system.

  4. A resonance enhancement of the phase relaxation in the electron spin echo of nitroxide covalently attached to cytochrome c

    NASA Astrophysics Data System (ADS)

    Hilczer, W.; Goslar, J.; Gramza, M.; Hoffmann, S. K.; Blicharski, W.; Osyczka, A.; Turyna, B.; Froncisz, W.

    1995-12-01

    The spin lattice T1 and phase memory TM relaxation times were measured by an electron spin echo technique for the nitroxide spin label attached covalently to horse heart cytochrome c below 80 K for oxidized (Fe 3+) and reduced (Fe 2+) samples. T1 decreases on heating and below 10 K is governed by the direct relaxation process for the reduced sample. The spin-lattice relaxation is enhanced by a cross-relaxation to Fe 3+ in an oxidized sample. In the TM temperature dependence an unusual deep minimum appears at about 25 K. This resonance type effect which vanishes completely for the reduced sample is due to a coupling to the Fe 3+ spins. The spin-lattice relaxation rate of Fe 3+ is comparable to the TM of nitroxide at low temperature producing a minimum in TM when the Ti value corresponds to the spin packet width of excited spins.

  5. Angular dependence of dissociative electron attachment topolyatomic molecules: application to the 2B1 metastable state of the H2Oand H2S anions

    SciTech Connect

    Haxton, Daniel J.; McCurdy, C. William; Rescigno, Thomas N.

    2006-01-12

    The angular dependence of dissociative electron attachment (DEA) to polyatomic targets is formulated in the local complex potential model, under the assumption that the axial recoil approximation describes the dissociation dynamics. An additional approximation, which is found to be valid in the case of H2O but not in the case of H2S, makes it possible to describe the angular dependence of DEA solely from an analysis of the fixed-nuclei entrance amplitude, without carrying out nuclear dynamics calculations. For H2S, the final-vibrational-state-specific angular dependence of DEA is obtained by incorporating the variation of the angular dependence of the entrance amplitude with nuclear geometry into the nuclear dynamics. Scattering calculations using the complex Kohn method and, for H2S, full quantum calculations of the nuclear dynamics using the Multi-Configuration Time-Dependent Hartree method, are performed.

  6. Specific anion effects on the pressure dependence of the protein-protein interaction potential.

    PubMed

    Möller, Johannes; Grobelny, Sebastian; Schulze, Julian; Steffen, Andre; Bieder, Steffen; Paulus, Michael; Tolan, Metin; Winter, Roland

    2014-04-28

    We present a study on ion specific effects on the intermolecular interaction potential V(r) of dense protein solutions under high hydrostatic pressure conditions. Small-angle X-ray scattering in combination with a liquid-state theoretical approach was used to determine the effect of structure breaking/making salt anions (Cl(-), SO4(2-), PO4(3-)) on the intermolecular interaction of lysozyme molecules. It was found that besides the Debye-Hückel charge screening effect, reducing the repulsiveness of the interaction potential V(r) at low salt concentrations, a specific ion effect is observed at high salt concentrations for the multivalent kosmotropic anions, which modulates also the pressure dependence of the protein-protein interaction potential. Whereas sulfate and phosphate strongly influence the pressure dependence of V(r), chloride anions do not. The strong structure-making effect of the multivalent anions, dominating for the triply charged PO4(3-), renders the solution structure less bulk-water-like at high salt concentrations, which leads to an altered behavior of the pressure dependence of V(r). Hence, the particular structural properties of the salt solutions are able to influence the spatial organization and the intermolecular interactions of the proteins, in particular upon compression. These results are of interest for exploring the combined effects of ionic strength, temperature and pressure on the phase behavior of protein solutions, but may also be of relevance for understanding pressure effects on the hydration behavior of biological matter under extreme environmental conditions. PMID:24626853

  7. Pressure dependence of quality factors of graphene nano-mechanical resonators

    NASA Astrophysics Data System (ADS)

    Khaksaran, M. Hadi; Yanik, Cenk; Karakan, M. Cagatay; Ari, Atakan Bekir; Hanay, M. Selim; Kaya, Ismet I.

    In recent few years, low mass density and high stiffness of graphene has drawn attention for developing high frequency mechanical resonators with high quality factor at the same time. As a single-atom thick material, graphene has many desirable properties for high-frequency sensor applications compared to top-down nano-mechanical resonators . In this work we address the energy dissipation in graphene resonators due to viscous damping. We experimentally measure the pressure dependence of the quality factor of a graphene nano-mechanical resonator to understand its interaction with fluids at high frequencies. This work is supprted by TUBITAK under Grant Number 112T990.

  8. Pressure dependence of structural and dynamical properties in melt sulfur: Evidence for two successive chain breakages

    NASA Astrophysics Data System (ADS)

    Zhao, G.; Mu, H. F.

    2014-11-01

    Using ab initio molecular dynamics simulations, the pressure dependence of structural and dynamical properties in melt sulfur along 1085 K isotherm was studied with pressure range from 4.18 to 15.8 GPa. It was found that the atomic chains in melt sulfur abruptly break twice with increasing pressure. The electric density of state near EF and the diffusion coefficient both show abrupt increase along with these two times of breakages. These changes would strongly influence the physical properties such as conductivity and viscosity. However, the density discontinuity along the isotherm, indication of a first-order phase transition, was not found.

  9. Electronic transport in oligo-para-phenylene junctions attached to carbon nanotube electrodes: Transition-voltage spectroscopy and chirality

    SciTech Connect

    Brito Silva, C. A. Jr.; Silva, S. J. S. da; Leal, J. F. P.; Pinheiro, F. A.; Del Nero, J.

    2011-06-15

    We have investigated, by means of a nonequilibrium Green's function method coupled to density functional theory, the electronic transport properties of molecular junctions composed of oligo-para-phenylene (with two, three, four, and five phenyl rings) covalently bridging the gap between metallic carbon nanotubes electrodes. We have found that the current is strongly correlated to a purely geometrical chiral parameter, both on-resonance and off-resonance. The Fowler-Nordheim plot exhibits minima, V{sub min}, that occur whenever the tail of a resonant transmission peak enters in the bias window. This result corroborates the scenario in which the coherent transport model gives the correct interpretation to transition voltage spectroscopy (TVS). We have shown that V{sub min} corresponds to voltages where a negative differential resistance (NDR) occurs. The finding that V{sub min} corresponds to voltages that exhibit NDR, which can be explained only in single-molecule junctions within the coherent transport model, further confirms the applicability of such models to adequately interpret TVS. The fact that the electrodes are organic is at the origin of differences in the behavior of V{sub min} if compared to the case of molecular junctions with nonorganic contacts treated so far.

  10. Excess Electron Attachment Induces Barrier-Free Proton Transfer in Anionic Complexes of Thymine and Uracil with Formic Acid

    SciTech Connect

    Haranczyk, Maciej; Dabkowska, Iwona; Rak, Janusz; Gutowski, Maciej S.; Nilles, J.M.; Stokes, Sarah; Radisic, Dunja; Bowen, Kit H.

    2004-06-03

    The anionic complexes of formic acid with uracil and thymine reveal broad features in photoelectron spectroscopy (PES) experiments with maxima at 1.7 and 1.1 eV, respectively. The results of quantum chemical calculations suggest that electron vertical detachment energies (VDE) of 1.6-1.9 eV correspond to anionic structures in which a proton has been transferred from the carboxylic group of the formic acid to the O8 atom of uracil or thymine. Smaller values of VDE (0.8 to 1.3 eV) correspond to chemically untransformed complexes, in which anionic uracil or thymine interacts through two hydrogen bonds with the carboxylic group of the intact formic acid. The recorded spectra and the results of quantum chemical calculations suggest that both nucleic acid bases undergo barrier-free proton transfer in anionic complexes with formic acid. The difference in experimental spectra of UF- and TF- provides an indication that the methyl group of thymine could make a difference in the intermolecular proton transfer.

  11. Pressure dependence of the boson peak in glasses: Correlated and uncorrelated perturbations

    NASA Astrophysics Data System (ADS)

    Schober, H. R.; Buchenau, U.; Gurevich, V. L.

    2014-01-01

    The pressure dependence of the boson peak in glasses within the framework of the extended soft potential model is reconsidered, taking effects at small pressures into account. One of these is the pressure dependence of the elastic constants, changing the interaction between the soft localized modes and thus changing the quasilocalized vibrations (QLVs) of the boson peak. This and other effects require the introduction of additional parameters to describe all the different influences of the pressure in detail. As in the first treatment of the problem, the dominating high-pressure influence remains the creation of pressure forces, which have to be added to the random forces responsible for the boson peak formation. The pressure forces consist of a correlated and an uncorrelated part (correlated with respect to the already existing random forces). Both lead to the P1/3 dependence observed in high-pressure experiments, but the uncorrelated part vanishes at small pressure P. The comparison to experiment is divided into a small pressure part, accessible through low-temperature heat capacity and thermal expansion measurements, and the high-pressure part, mostly Raman scattering measurements of the boson peak under pressure. The results suggest that the latter are dominated by the uncorrelated part of the forces, probably due to pressure-induced relaxations.

  12. Pressure dependence of the local structure of iridium ditelluride across the structural phase transition

    NASA Astrophysics Data System (ADS)

    Paris, E.; Joseph, B.; Iadecola, A.; Marini, C.; Ishii, H.; Kudo, K.; Pascarelli, S.; Nohara, M.; Mizokawa, T.; Saini, N. L.

    2016-04-01

    The local structure of IrTe2 has been studied by iridium L3-edge x-ray absorption spectroscopy (XAS) measurements as a function of pressure, performed at two temperatures (100 and 295 K) across the structural phase transition at ˜270 K. Extended x-ray absorption fine structure (EXAFS) and x-ray absorption near-edge structure (XANES) spectra show pressure-dependent anomalies, suggesting phase transitions that are characterized by different local atomic displacements. The high-temperature phase of IrTe2 (trigonal at 295 K) reveals a clear anomaly in the Ir-Te correlations at ˜4 GPa, while the low-temperature phase (at 100 K) shows a smaller change at ˜6 GPa, likely to be associated with transitions in lower-symmetry phases. XANES spectra, measuring higher-order atomic correlations, also show nonlinear pressure dependence in the local geometry at the anomalous pressures. These nonlinear changes suggest that IrTe2 goes through lower local symmetry phases with increasing pressure.

  13. Pressure-dependent Raman spectra of β-Ca3(PO4)2 whitlockite

    NASA Astrophysics Data System (ADS)

    Zhai, Shuangmeng; Wu, Xiang; Xue, Weihong

    2015-04-01

    The pressure dependence of Raman spectra for whitlockite β-Ca3(PO4)2 was investigated up to 18.0 GPa using a diamond-anvil cell at room temperature. The Raman frequencies of all observed bands for β-Ca3(PO4)2 continuously increase with increasing pressure. The quantitative analysis of pressure dependence of Raman bands for the sample shows that the ν 3 asymmetric and ν 1 symmetric stretching vibrations are with the larger pressure coefficients (from 3.44 to 4.59 cm-1 GPa-1) and that the ν 4 bending and ν 2 deforming vibrations are with the smaller pressure coefficients (from 1.46 to 3.12 cm-1 GPa-1). Combined with previous result, the isothermal mode Grüneisen parameters of β-Ca3(PO4)2 were calculated. The splitting of the PO4 symmetric stretching ν 1 vibrations changes during compression and disappears around 15.4 GPa, which may be attributed to the evolution of PO4 tetrahedra under high pressure.

  14. Pressure dependence of the optical properties of the charge-density-wave compound LaTe2

    SciTech Connect

    Lavagnini, M.; Sacchetti, A.; Degiorgi, L.; Arcangeletti, E.; Baldassarre, L.; Postorino, P.; Lupi, S.; Perucchi, A.; Shin, K.Y.; Fisher, I.R.; /Stanford U., Geballe Lab.

    2009-12-14

    We report the pressure dependence of the optical response of LaTe{sub 2}, which is deep in the charge-density-wave (CDW) ground state even at 300 K. The reflectivity spectrum is collected in the mid-infrared spectral range at room temperature and at pressures between 0 and 7 GPa. We extract the energy scale due to the single particle excitation across the CDW gap and the Drude weight. We establish that the gap decreases upon compressing the lattice, while the Drude weight increases. This signals a reduction in the quality of nesting upon applying pressure, therefore inducing a lesser impact of the CDW condensate on the electronic properties of LaTe{sub 2}. The consequent suppression of the CDW gap leads to a release of additional charge carriers, manifested by the shift of weight from the gap feature into the metallic component of the optical response. On the contrary, the power-law behavior, seen in the optical conductivity at energies above the gap excitation and indicating a weakly interacting limit within the Tomonaga-Luttinger liquid scenario, seems to be only moderately dependent on pressure.

  15. Mesospheric removal of very long-lived greenhouse gases SF6 and CFC-115 by metal reactions, Lyman-α photolysis, and electron attachment.

    PubMed

    Totterdill, Anna; Kovács, Tamás; Gómez Martín, Juan Carlos; Feng, Wuhu; Plane, John M C

    2015-03-12

    The fluorinated gases SF6 and C2F5Cl (CFC-115) are chemically inert with atmospheric lifetimes of many centuries which, combined with their strong absorption of IR radiation, results in unusually high global warming potentials. Very long lifetimes imply that mesospheric sinks could make important contributions to their atmospheric removal. In order to investigate this, the photolysis cross sections at the prominent solar Lyman-α emission line (121.6 nm), and the reaction kinetics of SF6 and CFC-115 with the neutral meteoric metal atoms Na, K, Mg, and Fe over large temperature ranges, were measured experimentally. The Na and K reactions exhibit significant non-Arrhenius behavior; quantum chemistry calculations of the potential energy surfaces for the SF6 reactions indicate that the Na and K reactions with SF6 are probably activated by vibrational excitation of the F-SF5 (v3) stretching mode. A limited set of kinetic measurements on Na + SF5CF3 are also presented. The atmospheric removal of these long-lived gases by a variety of processes is then evaluated. For SF6, the removal processes in decreasing order of importance are electron attachment, VUV photolysis, and reaction with K, Na, and H. For CFC-115, the removal processes in decreasing order of importance are reaction with O((1)D), VUV photolysis, and reaction with Na, K, and H. PMID:25647411

  16. Pressure-dependent structures of amorphous red phosphorus and the origin of first sharp diffraction peaks.

    NASA Astrophysics Data System (ADS)

    Zaug, Joseph; Soper, Alan; Clark, Simon

    2009-03-01

    Characterizing the nature of medium range order (MRO) in liquids and disordered solids is important for understanding their structure and transport properties. However, accurately portraying MRO, as manifested by the first sharp diffraction peak (FSDP) in neutron and X-ray scattering measurements, has remained elusive for more than 80 years. Here, using X-ray diffraction of amorphous red phosphorus (a-rP) compressed to 6.30 GPa, supplemented with micro-Raman scattering studies, we build three-dimensional structural models consistent with the diffraction data. We discover that the pressure dependence of the FSDP intensity and line position can be quantitatively accounted for by a characteristic void distribution function, defined in terms of average void-size, void-spacing, and void-density. This work provides a template to unambiguously interpret atomic and void-space MRO across a broad range of technologically promising network-forming materials.

  17. Monte Carlo simulations of the pressure dependence of the water-acid gas interfacial tensions.

    PubMed

    Biscay, F; Ghoufi, A; Lachet, V; Malfreyt, P

    2009-10-29

    We report two-phase Monte Carlo (MC) simulations of the binary water-acid gas mixtures at high temperature and high pressure. Simulations are performed in the Np(N)AT ensemble in order to reproduce the pressure dependence of the interfacial tensions of the water-CO(2) and water-H(2)S mixtures. The interfacial tension of the binary water-CO(2) mixture is determined from 5 to 45 MPa along the isotherm T = 383 K. Water-H(2)S interfacial tensions are computed along one supercritical isotherm (T = 393 K) in a pressure range of 1-15 MPa. The temperature and pressure conditions investigated here by the MC simulations are typical of the geological storage conditions of these acid gases. The coexisting densities and the compositions of the water-rich and acid-gas-rich phases are compared with experiments and with data calculated from Gibbs ensemble Monte Carlo (GEMC) simulations. PMID:19803493

  18. Pressure-dependent Raman scattering and photoluminescence of Zn1-xCdxSe epilayers

    NASA Astrophysics Data System (ADS)

    Lin, Y. C.; Chiu, C. H.; Fan, W. C.; Yang, S. L.; Chuu, D. S.; Chou, W. C.

    2007-04-01

    Raman and photoluminescence spectra of cubic Zn1-xCdxSe (0≦x≦0.32) epilayers were obtained at high pressure. The impurity mode I observed in the phonon Raman spectra at low temperature confirms the intermediate phonon mode behavior. A split transverse optical phonon mode was found in the down-stroke high-pressure Raman scattering. Additionally, the pressure-dependent longitudinal optical (LO) phonon frequencies and the Grüneisen parameter (γLO) were obtained by quadratic polynomial fitting. Pressure-driven resonant Raman scattering effect was observed in samples with a high Cd concentration (x≧0.18). The critical pressure of semiconductor-to-metal phase transition (Pt) decreases as the Cd content increases. As the Cd concentration increases from 0 to 0.32, Pt falls from 13.6to9.4GPa, according to Pt (GPa)=13.6-6.8x-20.3x2.

  19. Goddard rattler-jamming mechanism for quantifying pressure dependence of elastic moduli of grain packs

    SciTech Connect

    Pride, Steven R.; Berryman, James G.

    2009-01-05

    An analysis is presented to show how it is possible for unconsolidated granular packings to obey overall non-Hertzian pressure dependence due to the imperfect and random spatial arrangements of the grains in these packs. With imperfect arrangement, some gaps that remain between grains can be closed by strains applied to the grain packing. As these gaps are closed, former rattler grains become jammed and new stress-bearing contacts are created that increase the elastic stiffness of the packing. By allowing for such a mechanism, detailed analytical expressions are obtained for increases in bulk modulus of a random packing of grains with increasing stress and strain. Only isotropic stress and strain are considered in this analysis. The model is shown to give a favorable fit to laboratory data on variations in bulk modulus due to variations in applied pressure for bead packs.

  20. Critical Exponents and Pressure Dependence of Tc of La(Ca)MnO3

    NASA Astrophysics Data System (ADS)

    Souza, Jose A.; White, B. D.; Neumeier, J. J.; Yu, Y.-K.; Dos Santos, C. A. M.

    2007-03-01

    Measurements of heat capacity and thermal expansion for La1- xCaxMnO3 with x = 0, 0.20, 0.25, 0.30, 0.35, 0.40, 0.45, and 1 are reported. Using a model proposed previously (Souza et al. Phys. Rev. Lett. 94, 207209 (2005)), which utilizes both heat capacity (CP) and thermal expansion coefficient (μ) data, the pressure dependencies of Tc, dTc/dP, are obtained for all samples. dTc/dP decreases as the Ca doping increases. Critical behavior using both CP and μ is evaluated for the samples. The critical exponent α increases from 0.13, for LaMnO3 to 0.97 for x = 0.30. As Ca content is increased further, α drops reaching 0.11, for CaMnO3.

  1. Pressure dependent elastic constants of alpha and gamma cyclotrimethylene trinitramine: A quantum mechanical study

    SciTech Connect

    Taylor, DeCarlos E.

    2014-08-07

    The elastic constants of the α and γ polymorphs of cyclotrimethylene trinitramine (RDX) have been computed using dispersion corrected density functional theory (DFT). The DFT results validate the values obtained in several experiments using ultrasonic and impulsive stimulated thermal scattering techniques and disagree with those obtained using Brillouin scattering which, in general, exceed the other experimental and theoretical results. Compressibility diagrams at zero pressure are presented for the ab, ac, and bc crystallographic planes, and the anisotropic linear compressibility within the ac plane of α-RDX at 0 GPa, observed using ultrasonic and impulsive stimulated thermal scattering measurements, is verified using DFT. The pressure dependence of the elastic constants of α-RDX (0–4 GPa) and γ-RDX (4–8 GPa) is also presented.

  2. Pressure dependence on the reaction propagation rate of PETN at high pressure

    SciTech Connect

    Foltz, M.F.

    1993-04-01

    The reaction propagation rate (RPR) of the sensitive high explosive pentaerythritol tetranitrate (PETN) was measured in a diamond anvil cell (DAC) over the pressure range of 2--20 GPa. The experimental technique used is the same as that previously reported. The RPR data shows that it burns one to two orders of magnitude faster in the DAC than 1,3,5,-triamino-2,4,6-trinitrobenzene (TATB) and nitromethane (CH{sub 3}NO{sub 2}) respectively. The PETN RPR curve did not show sample pressure-dependent behavior like that of nitromethane, but instead varied abruptly like the RPR curve of TATB. In order to interpret these changes, static-pressure DAC mid-IR FTIR spectra were taken of micro-pellets of PETN embedded in KBr. The relationship between changes in the spectra, the RPR curve, and published single crystal PETN wedge test data are discussed.

  3. Temperature and pressure dependences of acoustic anomalies of PET films studied by using Brillouin spectroscopy

    NASA Astrophysics Data System (ADS)

    Ko, Young Ho; Kim, Kwang Joo; Lee, Byoung Wan; Jeong, Min-Seok; Ko, Jae-Hyeon

    2015-04-01

    The acoustic properties of biaxially-oriented polyethylene terephthalate (PET) were investigated as a function of either temperature or pressure by using Brillouin spectroscopy. The Brillouin frequency shift of the longitudinal acoustic mode of both biaxially-oriented and amorphous PET materials showed a change in the slope near 80 °C, which was the approximate glass transition temperature. The acoustic damping of amorphous PET exhibited large values near the melting temperature compared to that of semicrystalline PET. This indicated stronger coupling between the acoustic waves and the structural relaxation process in the amorphous state. The pressure dependences of the sound velocities were investigated at pressures up to 8.5 GPa by using a diamond anvil cell. The pressure-density relationship could be obtained based on the Birch-Murnaghan equation of state.

  4. Pressure Dependence and Metastable State Formation in the Photolysis of Dichlorine Monoxide (Cl2O)

    NASA Technical Reports Server (NTRS)

    Nickolaisen, Scott; Miller, Charles; Sander, Stanley; Hand, Michael; Williams, Ian; Francisco, Joseph

    1995-01-01

    Physics%K photolysis, dichlorine monoxide, pressure%U http://techreports.jpl.nasa.gov/1995/95-0924.pdfThe photodissociation of dichlorine monoxide (Cl2O) was studied using broadband flash photolysis to investigate the influence of variations in the photolysis wavelength domain, bath gas pressure, and bath gas identity on the yield and temporal dependence of the ClO product. ClO yields were independent of bath gas pressure when the photolysis spectral band extended to 200 nm (quartz cutoff) but for photolysis restricted to wavelengths longer than about 250 nm, ClO yields decreased with increasing bath gas pressure and there was a pressure-dependent delay in the formation of ClO.!.

  5. Pressure Dependence of Superconductivity in FeSe studied by DC Magnetic Measurements

    NASA Astrophysics Data System (ADS)

    Miyoshi, Kiyotaka; Mutou, Eriko; Morishita, Koh; Fujiwara, Kenji; Takeuchi, Jun

    2012-12-01

    Pressure dependence of superconductivity in FeSe has been investigated by DC magnetic measurements under high pressure up to 5 GPa using miniature diamond anvil cell combined with commercial SQUID magnetometer. The specimens with nominal composition FeSex (x = 0.80-1.00) were prepared from iron pieces and selenium shot firing at 1075 °C. The specimens containing no impurity phase of hexagonal FeSe were obtained for 0.80<=x<=0.96. For all of the specimens, it has been found that Tc increases in two steps by the application of pressure P, showing a local maximum of Tc~12 K at P~1 GPa, and Tc is nearly pressure independent above ~3 GPa. The maximum value Tcmax above 3 GPa is 15-20 K for 0.80<=x<=0.98 but ~25 K for x>=0.99.

  6. Pressure-dependent kinetics of initial reactions in iso-octane pyrolysis.

    PubMed

    Ning, HongBo; Gong, ChunMing; Li, ZeRong; Li, XiangYuan

    2015-05-01

    This study focuses on the studies of the main pressure-dependent reaction types of iso-octane (iso-C8H18) pyrolysis, including initial C-C bond fission of iso-octane, isomerization, and β-scission reactions of the alkyl radicals produced by the C-C bond fission of iso-octane. For the C-C bond fission of iso-octane, the minimum energy potentials are calculated at the CASPT2(2e,2o)/6-31+G(d,p)//CAS(2e,2o)/6-31+G(d,p) level of theory. For the isomerization and the β-scission reactions of the alkyl radicals, the optimization of the geometries and the vibrational frequencies of the reactants, transition states, and products are performed at the B3LYP/CBSB7 level, and their single point energies are calculated by using the composite CBS-QB3 method. Variable reaction coordinate transition state theory (VRC-TST) is used for the high-pressure limit rate constant calculation and Rice-Ramsperger-Kassel-Marcus/master equation (RRKM/ME) is used to calculate the pressure-dependent rate constants of these channels with pressure varying from 0.01-100 atm. The rate constants obtained in this work are in good agreement with those available from literatures. We have updated the rate constants and thermodynamic parameters for species involved in these reactions into a current chemical kinetic mechanism and also have improved the concentration profiles of main products such as C3H6 and C4H6 in the shock tube pyrolysis of iso-octane. The results of this study provide insight into the pyrolysis of iso-octane and will be helpful in the future development of branched paraffin kinetic mechanisms. PMID:25868004

  7. Pressure dependence of optical transitions in In{sub 0.15}Ga{sub 0.85}N/GaN multiple quantum wells

    SciTech Connect

    Shan, W.; Ager, J.W. III, and; Walukiewicz, W.; Haller, E.E. |; McCluskey, M.D.; Johnson, N.M.; Bour, D.P.

    1998-10-01

    The effects of hydrostatic pressure on optical transitions in In{sub 0.15}Ga{sub 0.85}N/GaN multiple quantum wells (MQW{close_quote}s) have been studied. The optical transition associated with confined electron and hole states in the MQW{close_quote}s was found to shift linearly to higher energy with pressure but exhibit a significantly weaker pressure dependence compared to bulklike thick epitaxial-layer samples. Similar pressure coefficients obtained by both photomodulation and photoluminescence measurements rule out the possibility of the transition involving localized states deep in the band gap. We found that the difference in the compressibility of In{sub x}Ga{sub 1{minus}x}N and GaN induces a tensile strain in the compressively strained In{sub x}Ga{sub 1{minus}x}N well layers, partially compensating the externally applied hydrostatic pressure. This mechanical effect is primarily responsible for the smaller pressure dependence of the optical transitions in the In{sub x}Ga{sub 1{minus}x}N/GaN MQW{close_quote}s. In addition, the pressure-dependent measurements allow us to identify a spectral feature observed at an energy below the GaN band gap. We conclude that this feature is due to transitions from ionized Mg acceptor states to the conduction band in the {ital p}-type GaN cladding layer rather than a confined transition in the MQW{close_quote}s. {copyright} {ital 1998} {ital The American Physical Society}

  8. Paternal Attachment, Parenting Beliefs and Children's Attachment

    ERIC Educational Resources Information Center

    Howard, Kimberly S.

    2010-01-01

    Relationships between fathers' romantic attachment style, parenting beliefs and father-child attachment security and dependence were examined in a diverse sample of 72 fathers of young children. Paternal romantic attachment style was coded based on fathers' endorsement of a particular style represented in the Hazan and Shaver Three-Category…

  9. Fetomaternal attachment and anchorage in the early diffuse epitheliochorial placenta of the camel (Camelus dromedarius). Light, transmission, and scanning electron microscopic study.

    PubMed

    Abd-Elnaeim, M M; Pfarrer, C; Saber, A S; Abou-Elmagd, A; Jones, C J; Leiser, R

    1999-01-01

    Placentae of 22 one-humped camel concepti with crown-rump lengths (CRL) ranging from 2.5 to 26 cm were studied. The placentae were processed for light, transmission and scanning electron microscopy of exposed surfaces and microvascular corrosion casts. In very early stages of pregnancy (2.5-4.5 cm CRL) three froms of fetomaternal interrelationship are described. (1) Precontact, where the mononuclear trophoblast cells are still separated from the uterine epithelium by a gap containing interareolar histotroph. Both fetal and maternal epithelia develop apical ectoplasmic pads in this location. (2) Apposition, where microvilli of the apical cell membrane of the trophoblast contact the uterine epithelium focally. Multinuclear trophoblast giant cells develop beside the population of already present mononuclear trophoblast cells. Uterine ectoplasmic pads can be observed. (3) Adhesion occurs when apical cell membranes of fetal and maternal epithelia adhere to each other closely, thus forming a 'normal' intercellular space of 20 nm width, without any intervening uterine luminal space. Microvillous interdigitation in this location varies from a non-microvillous 'smooth adhesion', to a distinctly villiform 'rough adhesion', and a 'semismooth adhesion' is achieved when trophoblastic microvilli make intimate contact with the non-microvillous uterine apical cell membranes of ectoplasmic pads. This fetomaternal attachment process is sufficient until the conceptus reaches approximately 9 cm CRL. Then, from 10 to 13 cm CRL, additional anchorage of the placenta to the endometrium is accomplished by the growth of temporary grooves and ridges of the allantochorion and the endometrium, which indent each other in a complementary fashion. The height of these groove-ridge structures increases gradually in 14 to 18 cm CRL fetuses, and they also widen at about 25 cm CRL, thus forming globular fetal troughs and irregular, thick maternal ridges. These together create units responsible for

  10. Temperature and pressure dependences of kimberlite melts viscosity (experimental-theoretical study)

    NASA Astrophysics Data System (ADS)

    Persikov, Eduard; Bykhtiyarov, Pavel; Cokol, Alexsander

    2016-04-01

    Experimental data on temperature and pressure dependences of viscosity of model kimberlite melts (silicate 82 + carbonate 18, wt. %, 100NBO/T = 313) have been obtained for the first time at 100 MPa of CO2 pressure and at the lithostatic pressures up to 7.5 GPa in the temperature range 1350 oC - 1950 oC using radiation high gas pressure apparatus and press free split-sphere multi - anvil apparatus (BARS). Experimental data obtained on temperature and pressure dependences of viscosity of model kimberlite melts at moderate and high pressures is compared with predicted data on these dependences of viscosity of basaltic melts (100NBO/T = 58) in the same T, P - range. Dependences of the viscosity of model kimberlite and basaltic melts on temperature are consistent to the exponential Arrenian equation in the T, P - range of experimental study. The correct values of activation energies of viscous flow of kimberlite melts have been obtained for the first time. The activation energies of viscous flow of model kimberlite melts exponentially increase with increasing pressure and are equal: E = 130 ± 1.3 kJ/mole at moderate pressure (P = 100 MPa) and E = 160 ± 1.6 kJ/mole at high pressure (P = 5.5 GPa). It has been established too that the viscosity of model kimberlite melts exponentially increases on about half order of magnitude with increasing pressures from 100 MPa to 7.5 GPa at the isothermal condition (1800 oC). It has been established that viscosity of model kimberlite melts at the moderate pressure (100 MPa) is lover on about one order of magnitude to compare with the viscosity of basaltic melts, but at high pressure range (5.5 - 7.5 GPa), on the contrary, is higher on about half order of magnitude at the same values of the temperatures. Here we use both a new experimental data on viscosity of kimberlite melts and our structural chemical model for calculation and prediction the viscosity of magmatic melts [1] to determine the fundamental features of viscosity of