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Sample records for jet-cooled molecular ions

  1. An Intense Slit Discharge Source of Jet-Cooled Molecular Ions and Radicals (T(sub rot) less than 30 K)

    NASA Technical Reports Server (NTRS)

    Anderson, David T.; Davis, Scott; Zwier, Timothy S.; Nesbitt, David J.

    1996-01-01

    A novel pulsed, slit supersonic discharge source is described for generating intense jet-cooled densities of radicals (greater than 10(exp 12)/cu cm) and molecular ions (greater than 10(exp 10)/cu cm) under long absorption path (80 cm), supersonically cooled conditions. The design confines the discharge region upstream of the supersonic expansion orifice to achieve efficient rotational cooling down to 30 K or less. The collisionally collimated velocity distribution in the slit discharge geometry yields sub-Doppler spectral linewidths, which for open-shell radicals reveals spin-rotation splittings and broadening due to nuclear hyperfine structure. Application of the slit source for high-resolution, direct IR laser absorption spectroscopy in discharges is demonstrated on species such as OH, H3O(+) and N2H(+).

  2. Jet-cooled molecular radicals in slit supersonic discharges: Sub-Doppler infrared studies of methyl radical

    NASA Astrophysics Data System (ADS)

    Davis, Scott; Anderson, David T.; Duxbury, Geoffrey; Nesbitt, David J.

    1997-10-01

    A novel high-intensity source of jet-cooled molecular radicals is described based on the combination of (i) slit supersonic expansions with (ii) pulsed electric discharges. The electrode bias configuration effectively confines the discharge to a region upstream of the supersonic expansion, which results both in efficient rotational cooling (Trot≈25 K) and high radical densities (>1014/cm3). In conjunction with direct absorption laser probe methods, this discharge source provides a general technique for high-resolution IR studies of jet-cooled radicals. Performance of the slit discharge system is demonstrated on v=1←0 rovibrational transitions in jet-cooled OH radicals, which indicate sub-Doppler linewidths (Δν≈100 MHz) when probed along the slit expansion axis. The enhanced spectral resolution of the slit discharge geometry is utilized to probe the v3=1←0 asymmetric CH stretch vibration-rotation spectra of CH3 radical. Under sub-Doppler conditions, spin-rotation splittings are fully resolved and nuclear hyperfine splittings partially resolved in all of the transitions, permitting the first measure of Fermi contact interactions [af″=-65.5(9) MHz, ɛbb″=-354(5) MHz, af'=-65(2) MHz, ɛbb'=-353(2) MHz] and therefore both the sign and magnitude of spin-polarization effects for CH3 under isolated gas-phase conditions. The results permit direct comparison with high level ab initio calculations, and highlight a clear trend in spin-polarization effects between condensed and gas-phase behavior.

  3. Thermal Management Using Pulsating Jet Cooling Technology

    NASA Astrophysics Data System (ADS)

    Alimohammadi, S.; Dinneen, P.; Persoons, T.; Murray, D. B.

    2014-07-01

    The existing methods of heat removal from compact electronic devises are known to be deficient as the evolving technology demands more power density and accordingly better cooling techniques. Impinging jets can be used as a satisfactory method for thermal management of electronic devices with limited space and volume. Pulsating flows can produce an additional enhancement in heat transfer rate compared to steady flows. This article is part of a comprehensive experimental and numerical study performed on pulsating jet cooling technology. The experimental approach explores heat transfer performance of a pulsating air jet impinging onto a flat surface for nozzle-to-surface distances 1 <= H/D <= 6, Reynolds numbers 1,300 <= Re <= 2,800 pulsation frequency 2Hz <= f <= 65Hz, and Strouhal number 0.0012 <= Sr = fD/Um <= 0.084. The time-resolved velocity at the nozzle exit is measured to quantify the turbulence intensity profile. The numerical methodology is firstly validated using the experimental local Nusselt number distribution for the steady jet with the same geometry and boundary conditions. For a time-averaged Reynolds number of 6,000, the heat transfer enhancement using the pulsating jet for 9Hz <= f <= 55Hz and 0.017 <= Sr <= 0.102 and 1 <= H/D <= 6 are calculated. For the same range of Sr number, the numerical and experimental methods show consistent results.

  4. Molecular ion photofragment spectroscopy

    SciTech Connect

    Bustamente, S.W.

    1983-11-01

    A new molecular ion photofragment spectrometer is described which features a supersonic molecular beam ion source and a radio frequency octapole ion trap interaction region. This unique combination allows several techniques to be applied to the problem of detecting a photon absorption event of a molecular ion. In particular, it may be possible to obtain low resolution survey spectra of exotic molecular ions by using a direct vibrational predissociation process, or by using other more indirect detection methods. The use of the spectrometer is demonstrated by measuring the lifetime of the O/sub 2//sup +/(/sup 4/..pi../sub u/) metastable state which is found to consist of two main components: the /sup 4/..pi../sub 5/2/ and /sup 4/..pi../sub -1/2/ spin components having a long lifetime (approx. 129 ms) and the /sup 4/..pi../sub 3/2/ and /sup 4/..pi../sub 1/2/ spin components having a short lifetime (approx. 6 ms).

  5. Charge exchange molecular ion source

    DOEpatents

    Vella, Michael C.

    2003-06-03

    Ions, particularly molecular ions with multiple dopant nucleons per ion, are produced by charge exchange. An ion source contains a minimum of two regions separated by a physical barrier and utilizes charge exchange to enhance production of a desired ion species. The essential elements are a plasma chamber for production of ions of a first species, a physical separator, and a charge transfer chamber where ions of the first species from the plasma chamber undergo charge exchange or transfer with the reactant atom or molecules to produce ions of a second species. Molecular ions may be produced which are useful for ion implantation.

  6. Stimulated emission pumping spectroscopy of jet-cooled C3

    NASA Astrophysics Data System (ADS)

    Rohlfing, Eric A.; Goldsmith, J. E. M.

    1989-06-01

    We report a dispersed fluorescence spectrum obtained for excitation of a ∑+u-∑+g vibronic band of C3 at 33 588 cm-1, part of a newly discovered electronic system. Rotationally resolved stimulated-emission-pumping spectra of jet-cooled C3 using this ∑+u intermediate state are presented for dumping to the 0v121 (1≤v2≤13) and 6v121 (1≤v2≤5) levels in the 1Σ+g ground state. Vibrational term energies, rotational constants, and l-type doubling parameters are determined for each level.

  7. Sub-Doppler Jet-Cooled Infrared Spectroscopy of ND2H2+ and ND3H+ in the NH Stretch Fundamental Modes

    NASA Astrophysics Data System (ADS)

    Chang, Chih-Hsuan; Nesbitt, David

    2014-06-01

    Sub-Doppler jet-cooled rovibrational spectra of ND3H+, ND2H2+, and NDH3+ ions in various fundamental NH modes were observed and analyzed using difference frequency generation infrared spectroscopy. The ions were generated in the concentration-modulation slit-jet expansion via a H3+ proton transfer mechanism in a discharge mixture of ND3/H2O and H2 gases. NH mode excitation in ND3H+ ion yielded a prominent Q branch feature and parallel band rotational structure. Rotational transitions were confirmed unambiguously by four-line ground state combination differences within frequency measurement accuracy (10 MHz). The band origin was determined to be 3316.8413(9) cm-1. Perturbation in the upper state was observed from analysis of residuals. In the case of ND2H2+, both NH symmetric (b-type) and anti-symmetric (c-type) modes were observed and assigned for the first time, yielding band origins of 3297.5440(1) and 3337.9050(1) cm-1, respectively. The intensity for the two fundamental bands was interpreted with simple context of a bond-dipole model. The present study provided high precision ground state rotational constants (A"=4.85675(4), B"=3.96829(4), C"=3.44667(6) cm-1), which should facilitate microwave searches for isotope-substituted ammonium ions in the regions of interstellar medium, such as dense molecular clouds or younger stellar objects.

  8. Jet-Cooled Emission Spectra of the Xylyl Radicals

    NASA Astrophysics Data System (ADS)

    Selco, J. I.; Carrick, P. G.

    1995-09-01

    Jet-cooled electronic emission spectra from ortho-, meta-, and para-xylyl (methylbenzyl) radicals have been recorded with a corona excited supersonic expansion (CESE) apparatus. A full vibronic analysis of the D1 → D0 transitions for all three isomers has been carried out, allowing for unambiguous assignments of the gas-phase ground state vibrational frequencies. For modes exhibiting progressions (numbering according to Green and Wilson) (11 (18a), 29 (6b), 10 (6a), 9 (1), 25 (3) and 5 (14) in ortho-xylyl; 10 (6b) in meta-xylyl; and 5 (1), 6 (6a), 3 (7a), and 17 (10a) in para-xylyl), anharmonicity constants are calculated and reported. Although CESE excitation of the xylenes (used in this study as precursors) did not result in the interconversion of isomers, it does occur along with homolytic methyl C-H bond dissociation during the formation of the radicals.

  9. High-resolution photoabsorption spectrum of jet-cooled propyne

    SciTech Connect

    Jacovella, U.; Holland, D. M. P.; Boyé-Péronne, S.; Joyeux, D.; Archer, L. E.; Oliveira, N. de; Nahon, L.; Lucchese, R. R.; Xu, Hong; Pratt, S. T.

    2014-09-21

    The absolute photoabsorption cross section of propyne was recorded between 62 000 and 88 000 cm{sup −1} by using the vacuum-ultraviolet, Fourier-transform spectrometer at the Synchrotron Soleil. This cross section spans the region including the lowest Rydberg bands and extends above the Franck-Condon envelope for ionization to the ground electronic state of the propyne cation, X{sup ~+}. Room-temperature spectra were recorded in a flowing cell at 0.9 cm{sup −1} resolution, and jet-cooled spectra were recorded at 1.8 cm{sup −1} resolution and a rotational temperature of ∼100 K. The reduced widths of the rotational band envelopes in the latter spectra reveal new structure and simplify a number of assignments. Although nf Rydberg series have not been assigned previously in the photoabsorption spectrum of propyne, arguments are presented for their potential importance, and the assignment of one nf series is proposed. As expected from previous photoelectron spectra, Rydberg series are also observed above the adiabatic ionization threshold that converge to the v{sub 3}{sup +} = 1 and 2 levels of the C≡C stretching vibration.

  10. Laser-cooled atomic ions as probes of molecular ions

    SciTech Connect

    Brown, Kenneth R.; Viteri, C. Ricardo; Clark, Craig R.; Goeders, James E.; Khanyile, Ncamiso B.; Vittorini, Grahame D.

    2015-01-22

    Trapped laser-cooled atomic ions are a new tool for understanding cold molecular ions. The atomic ions not only sympathetically cool the molecular ions to millikelvin temperatures, but the bright atomic ion fluorescence can also serve as a detector of both molecular reactions and molecular spectra. We are working towards the detection of single molecular ion spectra by sympathetic heating spectroscopy. Sympathetic heating spectroscopy uses the coupled motion of two trapped ions to measure the spectra of one ion by observing changes in the fluorescence of the other ion. Sympathetic heating spectroscopy is a generalization of quantum logic spectroscopy, but does not require ions in the motional ground state or coherent control of the ion internal states. We have recently demonstrated this technique using two isotopes of Ca{sup +} [Phys. Rev. A, 81, 043428 (2010)]. Limits of the method and potential applications for molecular spectroscopy are discussed.

  11. Laser spectroscopy and dynamics of the jet-cooled AsH2 free radical

    NASA Astrophysics Data System (ADS)

    He, Sheng-Gui; Clouthier, Dennis J.

    2007-04-01

    The ÃA12-X˜B12 electronic transition of the jet-cooled AsH2 free radical has been studied by laser-induced fluorescence (LIF), wavelength-resolved emission, and fluorescence lifetime measurements. The radical was produced by a pulsed electric discharge through a mixture of arsine (AsH3) and high pressure argon at the exit of a pulsed valve. Nine vibronic bands were identified by LIF spectroscopy in the 505-400nm region, including a long progression in the bending mode and two bands (101 and 101201) involving the excited state As-H symmetric stretch. Single vibronic level emission spectra showed similar activity in the bending and symmetric stretching frequencies of the ground state. High-resolution spectra of the 000 band exhibited large spin splittings and small, resolved arsenic hyperfine splittings, due to a substantial Fermi contact interaction in the excited state. The rotational constants obtained in the analysis gave effective molecular structures of r0″=1.5183(1)Å, θ0″=90.75(1)° and r0'=1.4830(1)Å, θ0'=123.10(2)°. The excited state fluorescence lifetimes vary dramatically with rovibronic state, from a single value of 1.4μs to many with lifetimes less than 10ns, behavior which the authors interpret as signaling the onset of a predissociative process near the zero-point level of the ground state.

  12. Dispersed Fluorescence Spectroscopy of Jet-Cooled Isobutoxy, 2-METHYL-1-BUTOXY, and Isopentoxy Radicals

    NASA Astrophysics Data System (ADS)

    Reza, Md Asmaul; Reilly, Neil J.; Alam, Jahangir; Mason, Amy; Liu, Jinjun

    2015-06-01

    It is well known that rate constants of certain reactions of alkoxy radicals, e.g., unimolecular dissociation (decomposition by C-C bond fission) and isomerization via 1,5 H-shift, are highly sensitive to the molecular structure. In the present and the next talks, we report dispersed fluorescence (DF) spectra of various alkoxy radicals obtained under supersonic jet-cooled conditions by pumping different vibronic bands of their tilde B ← tilde X laser induced fluorescence (LIF) excitation spectra. This talk focuses on the DF spectra of 2-methyl-1-propoxy (isobutoxy), 2-methyl-1-butoxy, and 3-methyl-1-butoxy (isopentoxy). In all cases, strong CO-stretch progressions were observed, as well as transitions to other vibrational levels, including low-frequency ones. Quantum chemical calculations were carried out to aid the assignment of the DF spectra. Franck-Condon factors were calculated using the ezSpectrum program. Wu, Q.; Liang, G.; Zu, L.; Fang, W. J. Phys. Chem A 2012, 116, 3156-3162. Lin, J.; Wu, Q.; Liang, G.; Zu, L.; Fang, W. RSC Adv. 2012, 2, 583-589. Liang, G.; Liu , C.; Hao, H.; Zu, L.; Fang, W. J. Phys. Chem. A 2013, 117, 13229- 13235. V. Mozhayskiy and A. I. Krylov, http://iopenshell.usc.edu/

  13. Fluorescence lifetimes of jet-cooled tryptophan: elimination of complications from 1La emission

    NASA Astrophysics Data System (ADS)

    Huang, Yuhui; Arnold, Steven; Sulkes, Mark

    1994-08-01

    Fluorescence lifetime measurements can be made on the decay of individual 'frozen' conformers of tryptophan analogs in supersonic gas expansions. These measurements have shown differences in single exponential lifetimes among conformers of a given analog, results which are strongly consistent with the presence of conformation-dependent charge transfer quenching. For jet cooled tryptophan, however, one of the conformers emits from 1La, thereby complicating any interpretation of the results. To remove this problem we considered tryptophan analogs with C-5 substituents, in which all the jet cooled conformers emit from 1Lb. We observed differences in conformer lifetimes similar to cases considered earlier. In the course of this work we discovered that, in contrast to tryptophan, 5- methoxytryptophan shows single exponential decay in solution. Based on additional data for jet cooled samples, we propose the most likely explanation to be substituent induced changes in conformer geometries and populations.

  14. Development of Broad Range Scan Capabilities with Jet Cooled Cavity Ringdown Spectroscopy

    NASA Astrophysics Data System (ADS)

    Codd, Terrance J.; Chen, Ming-Wei; Miller, Terry A.

    2011-06-01

    We have developed a technique for obtaining broad scans, >100 Cm-1, for jet cooled cavity ringdown spectroscopy (CRDS) spectra. Previously the scans of the jet cooled, CRDS apparatus were limited to <10 Cm-1 due to the use of a narrow linewidth radiation source. However, by coupling our jet cooled, CRDS apparatus with a moderate resolution (≃q 0.05 Cm-1) dye laser we are able to greatly increase our rate of data acquisition thereby gaining the capability to perform broad spectral surveys of jet cooled molecules. As a test of the capabilities of the technique we have scanned the tilde{A}-tilde{X} transition of NO_3 previously reported by Deev et al. at room temperature. We believe that this will be a very useful technique to search for transitions of cold molecules whose frequencies are not well known and which later can be studied using high resolution methods. A. Deev, J. Sommar, and M. Okumura, J. Chem. Phys. 122, 224305 (2005).

  15. Photodissociation resonances of jet-cooled NO2 at the dissociation threshold by CW-CRDS.

    PubMed

    Dupré, Patrick

    2015-05-01

    Around 398 nm, the jet-cooled-spectrum of NO2 exhibits a well identified dissociation threshold (D0). Combining the continuous-wave absorption-based cavity ringdown spectroscopy technique and laser induced fluorescence detection, an energy range of ∼25 cm(-1) is analyzed at high resolution around D0. In addition to the usual molecular transitions to long-lived energy levels, ∼115 wider resonances are observed. The position, amplitude, and width of these resonances are determined. The resonance width spreads from ∼0.006 cm(-1) (i.e., ∼450 ps) to ∼0.7 cm(-1) (∼4 ps) with large fluctuations. The identification of at least two ranges of resonance width versus the excess energy can be associated with the opening of the dissociation channels NO2→NO(X(2)Π1/2, v=0, J=1/2+O((3)P2) and NO2→NO(X(2)Π1/2, v=0, J=3/2)+O((3)P2). This analysis corroborates the existence of loose transition states close to the dissociation threshold as reported previously and in agreement with the phase space theory predictions as shown by Tsuchiya's group [Miyawaki et al., J. Chem. Phys. 99, 254-264 (1993)]. The data are analyzed in the light of previously reported frequency- and time-resolved data to provide a robust determination of averaged unimolecular dissociation rate coefficients. The density of reactant levels deduced (ρreac ∼ 11levels/cm(-1)) is discussed versus the density of transitions, the density of resonances, and the density of vibronic levels. PMID:25956098

  16. Molecular ion sources for low energy semiconductor ion implantation (invited)

    NASA Astrophysics Data System (ADS)

    Hershcovitch, A.; Gushenets, V. I.; Seleznev, D. N.; Bugaev, A. S.; Dugin, S.; Oks, E. M.; Kulevoy, T. V.; Alexeyenko, O.; Kozlov, A.; Kropachev, G. N.; Kuibeda, R. P.; Minaev, S.; Vizir, A.; Yushkov, G. Yu.

    2016-02-01

    Smaller semiconductors require shallow, low energy ion implantation, resulting space charge effects, which reduced beam currents and production rates. To increase production rates, molecular ions are used. Boron and phosphorous (or arsenic) implantation is needed for P-type and N-type semiconductors, respectively. Carborane, which is the most stable molecular boron ion leaves unacceptable carbon residue on extraction grids. A self-cleaning carborane acid compound (C4H12B10O4) was synthesized and utilized in the ITEP Bernas ion source resulting in large carborane ion output, without carbon residue. Pure gaseous processes are desired to enable rapid switch among ion species. Molecular phosphorous was generated by introducing phosphine in dissociators via 4PH3 = P4 + 6H2; generated molecular phosphorous in a pure gaseous process was then injected into the HCEI Calutron-Bernas ion source, from which P4+ ion beams were extracted. Results from devices and some additional concepts are described.

  17. Molecular ion sources for low energy semiconductor ion implantation (invited).

    PubMed

    Hershcovitch, A; Gushenets, V I; Seleznev, D N; Bugaev, A S; Dugin, S; Oks, E M; Kulevoy, T V; Alexeyenko, O; Kozlov, A; Kropachev, G N; Kuibeda, R P; Minaev, S; Vizir, A; Yushkov, G Yu

    2016-02-01

    Smaller semiconductors require shallow, low energy ion implantation, resulting space charge effects, which reduced beam currents and production rates. To increase production rates, molecular ions are used. Boron and phosphorous (or arsenic) implantation is needed for P-type and N-type semiconductors, respectively. Carborane, which is the most stable molecular boron ion leaves unacceptable carbon residue on extraction grids. A self-cleaning carborane acid compound (C4H12B10O4) was synthesized and utilized in the ITEP Bernas ion source resulting in large carborane ion output, without carbon residue. Pure gaseous processes are desired to enable rapid switch among ion species. Molecular phosphorous was generated by introducing phosphine in dissociators via 4PH3 = P4 + 6H2; generated molecular phosphorous in a pure gaseous process was then injected into the HCEI Calutron-Bernas ion source, from which P4(+) ion beams were extracted. Results from devices and some additional concepts are described. PMID:26932065

  18. Molecular ions, Rydberg spectroscopy and dynamics

    SciTech Connect

    Jungen, Ch.

    2015-01-22

    Ion spectroscopy, Rydberg spectroscopy and molecular dynamics are closely related subjects. Multichannel quantum defect theory is a theoretical approach which draws on this close relationship and thereby becomes a powerful tool for the study of systems consisting of a positively charged molecular ion core interacting with an electron which may be loosely bound or freely scattering.

  19. Cavity QED in a molecular ion trap

    SciTech Connect

    Schuster, D. I.; Bishop, Lev S.; Chuang, I. L.; DeMille, D.; Schoelkopf, R. J.

    2011-01-15

    We propose a class of experiments using rotational states of dipolar molecular ions trapped near an on-chip superconducting microwave cavity. Molecular ions have several advantages over neutral molecules for such cavity quantum electrodynamics experiments. In particular, ions can be loaded easily into deep rf traps and are held independent of their internal state. An analysis of the detection efficiency for, and coherence properties of, the molecular ions is presented. We discuss approaches for manipulating quantum information and performing high-resolution rotational spectroscopy using this system.

  20. Vibronic spectroscopy of jet-cooled hydrogen-bonded clusters

    NASA Astrophysics Data System (ADS)

    Gerhards, M.; Kimpfel, B.; Pohl, M.; Schmitt, M.; Kleinermanns, K.

    1992-07-01

    Mass-selected, two-photon resonant ionisation spectra of supersonically cooled p-cresol · (H 2O) n and phenol · (H 2O) n are reported. Cluster spectra with one, two and three water molecules attached can be unambiguously assigned. A monotonic shift of the electronic spectra with increasing cluster size is not observed here. The spectrum of p-cresol · (H 2O) 1, is red-shifted relative to the free p-cresol spectrum, while the p-cresol · (H 2O) 2,3 electronic origins are blue-shifted relative to p-cresol · (H 2O) 1 but still lie on the red side of the monomer. Simple, highest occupied molecular orbital—lowest unoccupied molecular orbital (HOMO—LUMO) considerations based on an initio calculations show that this can be explained by the inductive effect exerted on the O-atom of p-cresol, which acts as proton donor and acceptor in the H-bonding. The blue shift of n-π* transitions of H-bonded chromophores with carbonyl groups like CH 2O · (H 2O) 1 can be explained similarly. Vibrational spectra of supersonically cooled complexes of p-cresol with H 2O and CH 3OH were further analysed by dispersed fluorescence and stimulated emission, detected by two-colour ionisation dip. In p-cresol · (H 2O) 1, progressions of the intermolecular cluster stretch vibration and its combination bands with intramolecular cluster vibrations were observed with similar frequencies in the S 0 and S 1 states. In p-cresol · (H 2O) 3, further intense intermolecular bands arise, namely the hydrogen-bridge bending and torsion vibrations. This can be attributed to the lower symmetry of these clusters. Ab initio quantum chemical calculations show p-cresol · (H 2O) 3 to have a higher H-bond stretch frequency than p-cresol · (H 2O) 1, because its (unsymmetric) cyclic structure is more rigid. A characteristic pattern of CH 3 torsional bands in p-cresol is observed with complex structures due the CH 3 torsion—overall rotation interaction. Although their appearance is similar, the spacing of

  1. Peltier Refrigerators for Molecular Ion Sources

    NASA Astrophysics Data System (ADS)

    Hershcovitch, Ady

    2008-11-01

    Molecular ion sources have been considered for various applications. In particular, there is considerable effort to develop decaborane and octadecaborane ion sources for the semiconductor industry. Since the invention of the transistor, the trend has been to miniaturize semiconductor devices. As semiconductors become smaller (and get miniaturized), ion energy needed for implantation decreases, since shallow implantation is desired. But, due to space charge (intra-ion repulsion) effects, forming and transporting ion beams becomes a rather difficult task. These problems associated with lower energy ion beams limit implanter ion currents, thus leading to low production rates. One way to tackle the space charge problem is to use singly charged molecular ions. A crucial aspect in generating large molecular ion beam currents is ion source temperature control. Peltier coolers, which have in the past successfully utilized in BaF2 and CSI gamma ray detectors, may be ideal for this application. Clogging prevention of molecular ion sources is also a hurdle, which was overcome with special slots. Both topics are to be presented.

  2. Jet-Cooled Spectroscopy on the Ailes Infrared Beamline of the Synchrotron Radiation Facility Soleil

    NASA Astrophysics Data System (ADS)

    Georges, Robert

    2015-06-01

    . Vervloet, Phys. Chem. Chem. Phys. 15, 10141-10150 (2013) The cyclic ground state structure of the HF trimer revealed by far-infrared jet-cooled Fourier transform spectroscopy. P. Asselin, P. Soulard, B. Madebène, M. Goubet, T. R. Huet, R. Georges, O. Pirali and P. Roy, Phys. Chem. Chem. Phys. 16(10), 4797-806 (2014) Standard free energy of the equilibrium between the trans-monomer and the cyclic-dimer of acetic acid in the gas phase from infrared spectroscopy. M. Goubet, P. Soulard, O. Pirali, P. Asselin, F. Réal, S. Gruet, T. R. Huet, P. Roy and R. Georges, Phys. Chem. Chem. Phys. DOI: 10.1039/c4cp05684a

  3. n,. pi. /sup */ state of jet-cooled benzophenone as studied by sensitized phosphorescence excitation spectroscopy

    SciTech Connect

    Kamei, S.; Sato, T.; Mikami, N.; Ito, M.

    1986-10-23

    The sensitized phosphorescence excitation spectrum of jet-cooled benzophenone due to the S/sub 1/(n,..pi../sup */) produced from S/sub 0/ transition has been measured. It was found that the spectrum consists exclusively of several long progressions of 60 cm/sup -1/ which is the in-phase torsional mode of the phenyl rings. The vibrational analysis and the potential calculation shows that the in the S/sub 1/(n,..pi../sup */) state great geometry changes occur in the dihedral angle between the phenyl rings, the C=O bond distance, and the C-C bonds adjacent to the C=O bond.

  4. Secondary ion mass spectrometry of MCsn+molecular ion complexes

    NASA Astrophysics Data System (ADS)

    Saha, Biswajit; Chakraborty, Purushottam

    2007-05-01

    Excellent detection sensitivity, high dynamic range and good depth resolution make the SIMS technique extremely powerful for the analysis of surfaces and interfaces. However, a serious problem in SIMS analysis is its "matrix effect" that hinders the quantification of a certain species in a sample and consequently, probing the composition of surfaces or interfaces by SIMS is greatly hindered. Appropriate corrective measures are therefore, needed to calibrate the secondary ion currents into respective concentrations for accurate compositional analysis. Working in the MCs+-SIMS mode (M - element to be analyzed, Cs+ - bombarding ions) can circumvent the matrix effect. The quantitative potential of the MCs+-SIMS method is understood by assuming that an MCs+ ion is generated by the combination of a secondary neutral M0 atom with a re-sputtered Cs+ ion in the near-surface region. The emission process for the species M0 is thus decoupled from the subsequent MCs+ ion formation process, in analogy with the ion formation in secondary neutral mass spectrometry (SNMS), resulting in a drastic decrease in matrix effect. Although this technique has found its applicability in direct quantification, it generally suffers from a low useful yield. In such cases, detection of MCsn+(n = 2, 3, …) molecular ions offers a better sensitivity as the yields of such molecular ion complexes have often been found higher than that of MCs+ ions. This is true in most of the cases where the elements are strongly electronegative with respect to cesium. Several works have been reported on the emission of MCsn+molecular ions in the SIMS process, but a complete understanding on the formation mechanism of these ion complexes is still lacking. The kinetic energy distributions of secondary MCsn+molecular ion complexes has been found to be an effective approach to estimate the local instantaneous surface work function changes under various surface exposure conditions, thereby enabling one to elucidate on

  5. Physics with fast molecular-ion beams

    SciTech Connect

    Kanter, E.P.

    1980-01-01

    Fast (MeV) molecular-ion beams provide a unique source of energetic projectile nuclei which are correlated in space and time. The recognition of this property has prompted several recent investigations of various aspects of the interactions of these ions with matter. High-resolution measurements on the fragments resulting from these interactions have already yielded a wealth of new information on such diverse topics as plasma oscillations in solids and stereochemical structures of molecular ions as well as a variety of atomic collision phenomena. The general features of several such experiments will be discussed and recent results will be presented.

  6. Molecular phosphorus ion source for semiconductor technology

    SciTech Connect

    Gushenets V. I.; Hershcovitch A.; Bugaev, A.S.; Oks, E.M.; Kulevoy, T.V.

    2012-02-15

    This paper presents results on the generation of molecular phosphorus ion beams in a hot filament ion source. Solid red phosphorous is evaporated mainly as tetra-atomic molecules up to a temperature of 800 C. Thus, one of the main conditions for producing maximum P{sub 4}{sup +} fraction in the beam is to keep the temperature of the phosphorous oven, the steam line and the discharge chamber walls no greater than 800 C. The prior version of our ion source was equipped with a discharge chamber cooling system. The modified source ensured a P{sub 4}{sup +} ion beam current greater than 30% of the total beam current.

  7. Laser spectroscopy of jet-cooled NiF: Application of Hougen's approximate model for the low-lying electronic states

    NASA Astrophysics Data System (ADS)

    Arsenault, D. L.; Tokaryk, D. W.; Adam, A. G.; Linton, C.

    2016-06-01

    We have taken laser-induced fluorescence spectra of jet-cooled nickel monofluoride formed in a laser-ablation molecular beam source. Dispersed-fluorescence spectroscopy confirms predictions by Hougen (2011) that the parity assignments of levels in the Ω = 1 / 2 state 1570 cm-1 above the ground state should be reversed from those given in Krouti et al. (2002). The quality of the high-resolution spectra was sufficient to measure the [22.9]1.5-X1.5 band for five isotopologues of nickel and the [22.9]1.5-[0.25]0.5 band for molecules containing 58Ni and 60Ni. The spectral line positions for each isotopologue were fit to the Hamiltonian model given by Hougen, which was extended to allow for calculation of the parity-splitting parameter in the ground state.

  8. Pyrene measurements in sooting low pressure methane flames by jet-cooled laser-induced fluorescence.

    PubMed

    Wartel, M; Pauwels, J-F; Desgroux, P; Mercier, X

    2011-12-15

    This paper presents in detail the study we carried out concerning the pyrene measurement by jet-cooled laser-induced fluorescence (JCLIF) in different sooting low pressure methane flames. The aim of this paper is both to demonstrate the potentialities of this technique for the measurement of such moderately sized polycyclic aromatic hydrocarbons under sooting flame conditions and to provide new experimental data for the understanding and the development of chemical models of the soot formation processes. Several concentration profiles of pyrene measured in different sooting flame (various pressure and equivalence ratio) are presented. The validation of the JCLIF method for pyrene measurements is explained in detail as well as the calibration procedure, based on the standard addition method, which has been implemented for the quantification of the concentration profiles. Sensitivity lower than 1 ppb was obtained for the measurement of this species under sooting flame conditions. PMID:22029528

  9. Spectroscopic observation of jet-cooled 2,5-dichlorobenzyl radical generated by corona discharge

    NASA Astrophysics Data System (ADS)

    Yi, Eun Hye; Yoon, Young Wook; Lee, Sang Kuk

    2014-07-01

    Vibronically excited but jet-cooled 2,5-dichlorobenzyl radical was generated from 2,5-dichlorotoluene precursor in a large excess of helium carrier gas, from which the visible vibronic emission spectrum was recorded. From an analysis of the spectrum observed, it was found that the origin band shows larger shift to red than those expected from mono-substitutions, which has been discussed in terms of orientation of substituents. Also, the electronic energy of the D1 → D0 transition and vibrational mode frequencies at the ground electronic state of the 2,5-dichlorobenzyl radical were determined in comparison with the known vibrational data of precursor and ab initio calculations.

  10. Photodissociation resonances of jet-cooled NO{sub 2} at the dissociation threshold by CW-CRDS

    SciTech Connect

    Dupré, Patrick

    2015-05-07

    Around 398 nm, the jet-cooled-spectrum of NO{sub 2} exhibits a well identified dissociation threshold (D{sub 0}). Combining the continuous-wave absorption-based cavity ringdown spectroscopy technique and laser induced fluorescence detection, an energy range of ∼25 cm{sup −1} is analyzed at high resolution around D{sub 0}. In addition to the usual molecular transitions to long-lived energy levels, ∼115 wider resonances are observed. The position, amplitude, and width of these resonances are determined. The resonance width spreads from ∼0.006 cm{sup −1} (i.e., ∼450 ps) to ∼0.7 cm{sup −1} (∼4 ps) with large fluctuations. The identification of at least two ranges of resonance width versus the excess energy can be associated with the opening of the dissociation channels NO{sub 2}→NO(X {sup 2}Π{sub 1/2}, v=0, J=1/2)+O({sup 3}P{sub 2}) and NO{sub 2}→NO(X {sup 2}Π{sub 1/2}, v=0, J=3/2)+O({sup 3}P{sub 2}). This analysis corroborates the existence of loose transition states close to the dissociation threshold as reported previously and in agreement with the phase space theory predictions as shown by Tsuchiya’s group [Miyawaki et al., J. Chem. Phys. 99, 254–264 (1993)]. The data are analyzed in the light of previously reported frequency- and time-resolved data to provide a robust determination of averaged unimolecular dissociation rate coefficients. The density of reactant levels deduced (ρ{sub reac} ∼ 11 levels/cm{sup −1}) is discussed versus the density of transitions, the density of resonances, and the density of vibronic levels.

  11. Dissociative Recombination of Molecular Ions for Astrochemistry

    NASA Astrophysics Data System (ADS)

    Savin, Daniel W.; Novotný, O.; Becker, A.; Buhr, H.; Geppert, W.; Hamberg, M.; Krantz, C.; Kreckel, H.; Schwalm, D.; Spruck, K.; Stützel, J.; Wolf, A.; Yang, B.

    2013-06-01

    Dissociative recombination (DR) of molecular ions is a key chemical process in the cold interstellar medium (ISM). DR affects the composition, charge state, and energy balance of such environments. Astrochemical models of the ISM require reliable total DR cross sections as well as knowledge of the chemical composition and excitation states of the neutral DR products. Theory cannot reliably provide these data. We have systematically measured DR for many astrophysically relevant molecular ions utilizing the TSR storage ring at the Max-Planck-Institute for Nuclear Physics in Heidelberg, Germany. We used the merged ion-electron beam technique combined with an energy- and position-sensitive imaging detector and are able to study DR down to plasma temperatures of 10 K. The DR count rate is used to obtain absolute DR rate coefficient. Additionally we determine the masses of the DR products by measuring their kinetic energy. This allows us to assign particular DR fragmentation channels and to obtain their branching ratios. Moreover, the distribution of detected fragment distances provides information on the kinetic energy released in DR and thus also on the internal excitation of the DR products. All this information is particularly important for understanding DR of heteronuclear polyatomic ions. We will present DR results for several ions recently investigated at TSR. This work is supported in part by NASA and the NSF.

  12. F 3 - molecular ions in fluoride crystals

    NASA Astrophysics Data System (ADS)

    Radzhabov, E. A.

    2016-02-01

    The UV absorption spectra of F 3 - molecular ions in LaF3, SrF2, CaF2, and BaF2 crystals doped with rare-earth elements are studied. Comparison of radiation-colored and additively colored crystals reveals the absorption bands of F 3 - hole centers in the region near 6 eV. Nonempirical calculations of optical transitions agree well with experimental results.

  13. Dissociative Recombination of Molecular Ions for Astrochemistry

    NASA Astrophysics Data System (ADS)

    Novotny, Oldrich; Becker, A.; Buhr, H.; Fleischmann, Andreas; Gamer, Lisa; Geppert, W.; Krantz, C.; Kreckel, H.; Schwalm, D.; Spruck, K.; Wolf, A.; Savin, Daniel Wolf

    2014-06-01

    Dissociative recombination (DR) of molecular ions is a key chemical process in the cold interstellar medium (ISM). DR affects the composition, charge state, and energy balance of such environments. Astrochemical models of the ISM require reliable total DR cross sections as well as knowledge of the chemical composition of the neutral DR products. We have systematically measured DR for many astrophysically relevant molecular ions utilizing the TSR storage ring at the Max-Planck-Institute for Nuclear Physics (MPIK) in Heidelberg, Germany. We used the merged ion-electron beam technique combined with an energy- and position-sensitive imaging detector and are able to study DR down to plasma temperatures as low as 10 K. The DR count rate is used to obtain an absolute merged beams DR rate coefficient from which we can derive a thermal rate coefficient needed for plasma models. Additionally we determine the masses of the DR products by measuring their kinetic energy in the laboratory reference frame. This allows us to assign particular DR fragmentation channels and to obtain their branching ratios. All this information is particularly important for understanding DR of heteronuclear polyatomic ions. We will present DR results for several ions recently investigated at TSR. A new Cryogenic Storage Ring (CSR) is currently being commissioned at MPIK. With the chamber cooled down to ~10 K and a base pressure better than 10-13 mbar, this setup will allow internal cooling of the stored ions down to their rotational ground states, thus opening a new era in DR experiments. New technological challenges arise due to the ultracold, ultra-high vacuum environment of the CSR and thus the detection techniques used at TSR cannot be easily transferred to CSR. We will present new approaches for DR fragment detection in cryogenic environment. This work is supported in part by NASA and the NSF.

  14. Vibronic Spectroscopy of Hetero Dihalo-Benzyl Radicals Generated by Corona Discharge : Jet-Cooled Chlorofluorobenzyl Radicals

    NASA Astrophysics Data System (ADS)

    Yoon, Young; Lee, Sang

    2015-06-01

    The technique of corona excited supersonic jet expansion coupled with a pinhole-type glass nozzle was applied to vibronic spectroscopy of jet-cooled chlorofluorobenzyl radicals for the vibronic assignments and measurements of electronic energies of the D_1 → D_0 transition. The vibronic emission spectra were recorded with a long-path monochromator in the visible region. The 2,3-, 2,4-, and 2.5-chlorofluorobenzyl radicals were generated by corona discharge of corresponding precursor molecules, chlorofluorotoluenes seeded in a large amount of helium carrier gas. The emission spectra show the vibronic bands originating from two benzyl-type radicals, chlorofluorobenzyl and fluorobenzyl benzyl radicals, in which fluorobenzyl radicals were obtained by displacement of Cl by H atom produced by the dissociation of methyl C-H bond. From an analysis of the spectra observed, we could determine the electronic energies in D_1 → D_0 transition and vibrational mode frequencies at the D_0 state of chlorofluorobenzyl radicals which show the origin band of the electronic transition to be shifted to red region, comparing with the parental benzyl radical. The red-shift is highly sensitive to the number, position, and kind of substituents in chlorofluorobenzyl radicals. From the quantitative analysis of the red-shift, it has been found that the additivity rule, discovered recently by Lee group predicts the observation very well. In addition, the negligible contribution of the substituent at the 4-position, the nodal point of the Hückel's molecular orbital theory, can be well describes by the disconnection of substituent from molecular plane of the benzene ring available for delocalized π electrons. In this presentation, I will discuss the spectroscopic observation of new chlorofluorobenzyl radicals and substituent effect on electronic transition energy which is useful for identification of isomeric substituted benzyl radicals. C.~S.~Huh, Y.~W.~Yoon, and S.~K.~Lee, J. Chem

  15. Resonant two-photon ionization spectroscopy of jet-cooled NiPt

    NASA Astrophysics Data System (ADS)

    Taylor, Scott; Spain, Eileen M.; Morse, Michael D.

    1990-03-01

    Resonant two-photon ionization spectroscopy of jet-cooled NiPt has been used to investigate the possibility of d-electron contributions to the bonding in this species. Based on an abrupt onset of predissociation, the bond strength of NiPt is assigned as D0(NiPt)=2.798±0.003 eV. Comparisons of scans using ArF (6.42 eV) or F2 (7.87 eV) radiation as the ionization laser yield IP(NiPt)=8.02±0.15 eV, from which we derive D0(Ni+-Pt)=2.41±0.15 eV and D0(Ni-Pt+) =3.58±0.35 eV. High resolution studies of the 6-0 and 8-0 bands of one of the three identifiable progressions demonstrate an Ω'=0←Ω`=0 transition with r'e =2.3396±0.0039Å and r″0 =2.2078±0.0023Å. The short bond length and large bond strength of NiPt, as compared to the corresponding values (re=2.330±0.003Å and D0=2.34±0.10 eV) for the coinage metal analog, CuAu, demonstrate significant d-orbital contributions to the bonding in NiPt.

  16. Laser-Induced Fluorescence Spectroscopy of Jet-Cooled t-Butoxy.

    PubMed

    Liu, Jinjun; Reilly, Neil J; Mason, Amy; Miller, Terry A

    2015-12-10

    The vibrational structures of the Ã(2)A1 and X̃(2)E states of t-butoxy were obtained in jet-cooled laser-induced fluorescence (LIF) and dispersed fluorescence (DF) spectroscopic measurements. The observed transitions are assigned based on vibrational frequencies calculated using the complete active space self-consistent field (CASSCF) method and the predicted Franck-Condon factors. The spin-orbit splitting was measured to be 36(5) cm(-1) for the lowest vibrational level of the ground (X̃(2)E) state, which is significantly smaller than that of methoxy, and increases with increasing vibrational quantum number of the CO stretch mode. Vibronic analysis of the DF spectra suggests that Jahn-Teller active modes of the ground-state t-butoxy radical are similar to those of methoxy and would be the same if methyl groups were replaced by hydrogen atoms. The rotational and fine structure of the LIF transition to the first CO stretch overtone level of the Ã(2)A1 state has been simulated using a spectroscopic model first proposed for methoxy, yielding an accurate determination of the rotational constants of both à and X̃ states. PMID:26524342

  17. Ground and excited state infrared spectroscopy of jet-cooled radicals: Exploring the photophysics of trihydronaphthyl and inden-2-ylmethyl

    NASA Astrophysics Data System (ADS)

    Kidwell, Nathanael M.; Mehta-Hurt, Deepali N.; Korn, Joseph A.; Sibert, Edwin L.; Zwier, Timothy S.

    2014-06-01

    The alkyl and aromatic CH stretch infrared spectra of inden-2-ylmethyl (I2M, C10H9) and trihydronaphthyl (THN, C10H11) radicals have been recorded under jet-cooled conditions in the ground (D0) and first electronically excited (D1) states using resonant ion-dip infrared (RIDIR) spectroscopy. Previously, the vibronic spectroscopy of a series of C10H9 and C10H11 hydronaphthyl radicals were investigated and their thermochemical properties were evaluated with isomer specificity [J. A. Sebree et al., J. Phys. Chem. A 11, 6255-6262 (2010)]. We show here that one of the m/z 129 spectral carriers characterized in that work was misidentified as 2-hydronaphthyl (2-HN) radical, appearing in a discharge of 1,2-dihydronaphthalene in close proximity to 1-hydronaphthyl radical. The D0-RIDIR spectrum in the alkyl CH stretch region positively identifies the m/z 129 isomer as I2M, whose two-color resonant two-photon ionization (2C-R2PI) spectrum was recently reported by Schmidt and co-workers [T. P. Troy et al., Chem. Sci. 2, 1755-1765 (2011)]. Here, we further characterize the I2M and THN radicals by recording their gas phase IR spectra in the alkyl and aromatic CH stretch regions, and explore the spectroscopic consequences of electronic excitation on the CH stretch absorptions. A local-mode CH stretch Hamiltonian incorporating cubic stretch-bend coupling between anharmonic CH stretches and CH2 scissor modes is utilized to describe their Fermi resonance interactions. Excellent agreement between the experimental and theoretical results facilitates the interpretation of the D0- and D1-state RIDIR spectra of I2M, revealing that upon excitation the alkyl CH stretches decrease in frequency by 70 cm-1, while the allyl-like CH stretches experience a modest blueshift. In comparison, the photophysics of THN are strikingly different in that the IR transitions that possess vibrational motion along the CβH and CδH bonds are absent in the D1-RIDIR spectrum yet are predicted to be present from

  18. Modeling ion sensing in molecular electronics

    NASA Astrophysics Data System (ADS)

    Chen, Caroline J.; Smeu, Manuel; Ratner, Mark A.

    2014-02-01

    We examine the ability of molecules to sense ions by measuring the change in molecular conductance in the presence of such charged species. The detection of protons (H+), alkali metal cations (M+), calcium ions (Ca2+), and hydronium ions (H3O+) is considered. Density functional theory (DFT) is used within the Keldysh non-equilibrium Green's function framework (NEGF) to model electron transport properties of quinolinedithiol (QDT, C9H7NS2), bridging Al electrodes. The geometry of the transport region is relaxed with DFT. The transport properties of the device are modeled with NEGF-DFT to determine if this device can distinguish among the M+ + QDT species containing monovalent cations, where M+ = H+, Li+, Na+, or K+. Because of the asymmetry of QDT in between the two electrodes, both positive and negative biases are considered. The electron transmission function and conductance properties are simulated for electrode biases in the range from -0.5 V to 0.5 V at increments of 0.1 V. Scattering state analysis is used to determine the molecular orbitals that are the main contributors to the peaks in the transmission function near the Fermi level of the electrodes, and current-voltage relationships are obtained. The results show that QDT can be used as a proton detector by measuring transport through it and can conceivably act as a pH sensor in solutions. In addition, QDT may be able to distinguish among different monovalent species. This work suggests an approach to design modern molecular electronic conductance sensors with high sensitivity and specificity using well-established quantum chemistry.

  19. Modeling ion sensing in molecular electronics

    SciTech Connect

    Chen, Caroline J.; Smeu, Manuel Ratner, Mark A.

    2014-02-07

    We examine the ability of molecules to sense ions by measuring the change in molecular conductance in the presence of such charged species. The detection of protons (H{sup +}), alkali metal cations (M{sup +}), calcium ions (Ca{sup 2+}), and hydronium ions (H{sub 3}O{sup +}) is considered. Density functional theory (DFT) is used within the Keldysh non-equilibrium Green's function framework (NEGF) to model electron transport properties of quinolinedithiol (QDT, C{sub 9}H{sub 7}NS{sub 2}), bridging Al electrodes. The geometry of the transport region is relaxed with DFT. The transport properties of the device are modeled with NEGF-DFT to determine if this device can distinguish among the M{sup +} + QDT species containing monovalent cations, where M{sup +} = H{sup +}, Li{sup +}, Na{sup +}, or K{sup +}. Because of the asymmetry of QDT in between the two electrodes, both positive and negative biases are considered. The electron transmission function and conductance properties are simulated for electrode biases in the range from −0.5 V to 0.5 V at increments of 0.1 V. Scattering state analysis is used to determine the molecular orbitals that are the main contributors to the peaks in the transmission function near the Fermi level of the electrodes, and current-voltage relationships are obtained. The results show that QDT can be used as a proton detector by measuring transport through it and can conceivably act as a pH sensor in solutions. In addition, QDT may be able to distinguish among different monovalent species. This work suggests an approach to design modern molecular electronic conductance sensors with high sensitivity and specificity using well-established quantum chemistry.

  20. High-Resolution Spectroscopy of Jet-Cooled Naphthalene: the 000 and 3301 Bands of the A~1B1u<--X~1Ag Transition

    NASA Astrophysics Data System (ADS)

    Joo, Duck-Lae; Takahashi, Rika; O'Reilly, John; Katô, Hajime; Baba, Masaaki

    2002-09-01

    Rotationally resolved excitation spectra of the 0 00 and 33 01 bands of the Ã1B1 u← X˜1Ag electronic transition of naphthalene were measured by a frequency-doubled single-mode tunable laser and a jet-cooled collimated molecular beam. The observed linewidth was 18 MHz, and the absolute wavenumber was determined with an accuracy of better than 0.0002 cm -1. The molecular constants of the X˜1Ag( v=0), Ã1B1 u( v=0), and Ã1B1 u( v33=1) levels were determined and represent the most accurate measurements to date. Three rotational constants were sufficient to fit 3386 lines of J=1-43 and Ka=0-21 with a standard deviation 0.0002 cm -1. This indicates that the molecular structures are rigid both in the X˜1Ag and Ã1B1 u states. When a magnetic field was applied, spectral line broadening was observed for levels with small Ka value in the Ã1B1 u( v33=1) state, and the Zeeman splitting was observed to increase with increasing J. No broadening, however, was observed in the 0 00 band up to H=0.65 T.

  1. Trapped ion simulation of molecular spectrum

    NASA Astrophysics Data System (ADS)

    Shen, Yangchao; Lu, Yao; Zhang, Kuan; Zhang, Shuaining; Huh, Joonsuk; Kim, Kihwan

    2016-05-01

    Boson sampling had been suggested as a classically intractable and quantum mechanically manageable problem via computational complexity theory arguments. Recently, Huh and co-workers proposed theoretically a modified version of boson sampling, which is designed to simulate a molecular problem, as a practical application. Here, we report the experimental implementation of the theoretical proposal with a trapped ion system. As a first demonstration, we perform the quantum simulation of molecular vibronic profile of SO2, which incorporates squeezing, rotation and coherent displacements operations, and the collective projection measurement on phonon modes. This work was supported by the National Basic Research Program of China 11CBA00300, 2011CBA00301, National Natural Science Foundation of China 11374178, 11574002. Basic Science Research Program of Korea NRF-2015R1A6A3A04059773.

  2. Molecular Turnstiles Regulated by Metal Ions.

    PubMed

    Wang, Guangxia; Xiao, Hongmei; He, Jiaojiao; Xiang, Junfeng; Wang, Ying; Chen, Xuebo; Che, Yanke; Jiang, Hua

    2016-04-15

    A family of novel molecular turnstiles 1-3 composed of two stators with pyridyl binding sites and a different-sized triptycene rotor was synthesized. The molecular turnstiles behave in an open state at room temperature in the absence of metal ions but display significantly different closed states in the presence of Ag(+) and Pd(2+). The Ag(+)-mediated turnstiles 1-3Ag exhibited closed states but unreadable bistability at ambient temperature because the Ag(+)-mediated macrocyclic framework is not able to restrict the rotations of the rotors; while temperature was decreased, the macrocyclic frameworks became stable enough to halt the rotations of the rotors, eventually leading to the readable closed states for 1-3Ag. In contrast, Pd(2+)-mediated macrocyclic frameworks are stable, giving rise to a detectable closed state of turnstiles 1-3Pd in a wide range of temperatures. These findings have also been supported by DFT calculations. PMID:26986992

  3. Collective effects in electronic sputtering of organic molecular ions by fast incident cluster ions

    SciTech Connect

    Salehpour, M.; Fishel, D.L.; Hunt, J.E.

    1988-07-15

    The collective sputtering effect of fast primary cluster ions on the yield of secondary molecular ions has been demonstrated for the first time. Results show that the sputtering yield of valine negative molecular ions per incident carbon atom, in a C/sup +//sub n/ incident cluster ion, increases with increasing n. The yield results are interpreted as a direct effect of the enhancement in the electronic stopping power per atom in cluster ions compared to atomic ions.

  4. Spectroscopy and electronic structure of jet-cooled NiPd and PdPt

    NASA Astrophysics Data System (ADS)

    Taylor, Scott; Spain, Eileen M.; Morse, Michael D.

    1990-03-01

    Resonant two-photon ionization spectroscopy of jet-cooled NiPd and PdPt has revealed a dense vibronic spectrum for NiPd and a much more sparse spectrum for PdPt. Four vibrational progressions have been identified for NiPd, and three have been located for PdPt. High resolution investigations of NiPd have established a ground state bond length of r″0 =2.242±0.005 Å with Ω″=2. The observed spectra have been used to bracket the ionization potentials, giving IP(NiPd)=7.18±0.76 eV and IP(PdPt)=8.27±0.38 eV. In contrast to previous work on Ni2, NiPt, and Pt2, no abrupt onset of rapid predissociation is observed for either NiPd or PdPt. A discussion of this result in terms of the expected potential energy curves for the palladium-containing diatomics is presented, which when combined with the frequencies of the highest energy vibronic bands observed yields estimates of D0(NiPd)≊1.46 eV and D0(PdPt)≊1.98 eV. The lack of observable vibronic transitions in Pd2 above 11 375 cm-1 places D0(Pd2) below 1.41 eV, in agreement with Knudsen effusion mass spectrometry. Finally a comparison of the platinum group dimers and the coinage metal dimers is given, demonstrating the increasing importance of d-orbital contributions to the bonding in the platinum group dimers as one moves down the periodic table. The anomalous behavior of the palladium-containing diatomics is also discussed in terms of the highly stable 4d105s0, 1S0 ground state of atomic palladium.

  5. Jet-Cooled Laser-Induced Fluorescence Spectroscopy of T-Butoxy

    NASA Astrophysics Data System (ADS)

    Reilly, Neil J.; Cheng, Lan; Stanton, John F.; Miller, Terry A.; Liu, Jinjun

    2015-06-01

    The vibrational structures of the tilde A ^2A_1 and tilde X ^2E states of t-butoxy were obtained in jet-cooled laser-induced fluorescence (LIF) and dispersed fluorescence (DF) spectroscopic measurements. The observed transitions are assigned based on vibrational frequencies calculated using Complete Active Space Self-Consistent Field (CASSCF) method and the predicted Franck-Condon factors. The spin-orbit (SO) splitting was measured to be 35(5) cm-1 for the lowest vibrational level of the ground (tilde X ^2E) state and increases with increasing vibrational quantum number of the CO stretch mode. Vibronic analysis of the DF spectra suggests that Jahn-Teller (JT)-active modes of the ground-state t-butoxy radical are similar to those of methoxy and would be the same if methyl groups were replaced by hydrogen atoms. Coupled-cluster calculations show that electron delocalization, introduced by the substitution of hydrogens with methyl groups, reduces the electronic contribution of the SO splittings by only around ten percent, and a calculation on the vibronic levels based on quasidiabatic model Hamiltonian clearly attributes the relatively small SO splitting of the tilde X ^2E state of t-butoxy mainly to stronger reduction of orbital angular momentum by the JT-active modes when compared to methoxy. The rotational and fine structure of the LIF transition to the first CO stretch overtone level of the tilde A^2A_1 state has been simulated using a spectroscopic model first proposed for methoxy, yielding an accurate determination of the rotational constants of both tilde A and tilde X states.

  6. Structure of the alkali-metal-atom + strontium molecular ions: Towards photoassociation and formation of cold molecular ions

    SciTech Connect

    Aymar, M.; Dulieu, O.; Guerout, R.

    2011-08-14

    The potential energy curves, permanent and transition dipole moments, and the static dipolar polarizability, of molecular ions composed of one alkali-metal atom and a strontium ion are determined with a quantum chemistry approach. The molecular ions are treated as effective two-electron systems and are treated using effective core potentials including core polarization, large gaussian basis sets, and full configuration interaction. In the perspective of upcoming experiments aiming at merging cold atom and cold ion traps, possible paths for radiative charge exchange, photoassociation of a cold lithium or rubidium atom and a strontium ion are discussed, as well as the formation of stable molecular ions.

  7. Vibrational Spectroscopy on Trapped Cold Molecular Ions

    NASA Astrophysics Data System (ADS)

    Khanyile, Ncamiso B.; Brown, Kenneth R.

    2014-06-01

    We perform vibrational spectroscopy on the V0←10 overtone of a trapped and sympathetically cooled CaH+ molecular ion using a resonance enhanced two photon dissociation scheme. Our experiments are motivated by theoretical work that proposes comparing the vibrational overtones of CaH^+ with electronic transitions in atoms to detect possible time variation of in the mass ratio of the proton to electron. Due to the nonexistence of experimental data of the transition, we start the search with a broadband femtosecond Ti:Saph laser guided by theoretical calculations. Once the vibrational transition has been identified, we will move to CW lasers to perform rotationally resolved spectroscopy. M. Kajita and Y. Moriwaki, J. Phys. B. At. Mol. Opt.Phys., 42,154022(2009) Private communication

  8. Jet-cooled laser-induced fluorescence spectroscopy of cyclohexoxy: rotational and fine structure of molecules in nearly degenerate electronic States.

    PubMed

    Liu, Jinjun; Miller, Terry A

    2014-12-26

    The rotational structure of the previously observed B̃(2)A' ← X̃(2)A″ and B̃(2)A' ← Ã(2)A' laser-induced fluorescence spectra of jet-cooled cyclohexoxy radical (c-C6H11O) [ Zu, L.; Liu, J.; Tarczay, G.; Dupré, P; Miller, T. A. Jet-cooled laser spectroscopy of the cyclohexoxy radical. J. Chem. Phys. 2004 , 120 , 10579 ] has been analyzed and simulated using a spectroscopic model that includes the coupling between the nearly degenerate X̃ and à states separated by ΔE. The rotational and fine structure of these two states is reproduced by a 2-fold model using one set of molecular constants including rotational constants, spin-rotation constants (ε's), the Coriolis constant (Aζt), the quenched spin-orbit constant (aζed), and the vibronic energy separation between the two states (ΔE0). The energy level structure of both states can also be reproduced using an isolated-state asymmetric top model with rotational constants and effective spin-rotation constants (ε's) and without involving Coriolis and spin-orbit constants. However, the spin-orbit interaction introduces transitions that have no intensity using the isolated-state model but appear in the observed spectra. The line intensities are well simulated using the 2-fold model with an out-of-plane (b-) transition dipole moment for the B̃ ← X̃ transitions and in-plane (a and c) transition dipole moment for the B̃ ← à transitions, requiring the symmetry for the X̃ (Ã) state to be A″ (A'), which is consistent with a previous determination and opposite to that of isopropoxy, the smallest secondary alkoxy radical. The experimentally determined Ã-X̃ separation and the energy level ordering of these two states with different (A' and A″) symmetries are consistent with quantum chemical calculations. The 2-fold model also enables the independent determination of the two contributions to the Ã-X̃ separation: the relativistic spin-orbit interaction (magnetic effect) and the nonrelativistic

  9. High-resolution spectroscopy of jet-cooled CH{sub 5}{sup +}: Progress

    SciTech Connect

    Savage, C.; Dong, F.; Nesbitt, D. J.

    2015-01-22

    Protonated methane (CH{sub 5}{sup +}) is thought to be a highly abundant molecular ion in interstellar medium, as well as a potentially bright μwave- mm wave emitter that could serve as a tracer for methane. This paper describes progress and first successful efforts to obtain a high resolution, supersonically cooled spectrum of CH{sub 5}{sup +} in the 2900-3100 cm{sup −1} region, formed in a slit supersonic discharge at low jet temperatures and with sub-Doppler resolution. Short term precision in frequency measurement (< 5 MHz on an hour time scale) is obtained from a thermally controlled optical transfer cavity servoloop locked onto a frequency stabilized HeNe laser. Long term precision (< 20 MHz day-to-day) due to pressure, temperature and humidity dependent index of refraction effects in the optical transfer cavity is also present and discussed.

  10. Numerical optimization of a multi-jet cooling system for the blown film extrusion

    NASA Astrophysics Data System (ADS)

    Janas, M.; Wortberg, J.

    2015-05-01

    The limiting factor for every extrusion process is the cooling. For the blown film process, this task is usually done by means of a single or dual lip air ring. Prior work has shown that two major effects are responsible for a bad heat transfer. The first one is the interaction between the jet and the ambient air. It reduces the velocity of the jet and enlarges the straight flow. The other one is the formation of a laminar boundary layer on the film surface due to the fast flowing cooling air. In this case, the boundary layer isolates the film and prevents an efficient heat transfer. To improve the heat exchange, a novel cooling approach is developed, called Multi-Jet. The new cooling system uses several slit nozzles over the whole tube formation zone for cooling the film. In contrast to a conventional system, the cooling air is guided vertically on the film surface in different heights to penetrate the boundary sublayer. Simultaneously, a housing of the tube formation zone is practically obtained to reduce the interaction with the ambient air. For the numerical optimization of the Multi-Jet system, a new procedure is developed. First, a prediction model identifies a worth considering cooling configuration. Therefore, the prediction model computes a film curve using the formulation from Zatloukal-Vlcek and the energy balance for the film temperature. Thereafter, the optimized cooling geometry is investigated in detail using a process model for the blown film extrusion that is able to compute a realistic bubble behavior depending on the cooling situation. In this paper, the Multi-Jet cooling system is numerically optimized for several different process states, like mass throughputs and blow-up ratios using one slit nozzle setting. For each process condition, the best cooling result has to be achieved. Therefore, the height of any nozzle over the tube formation zone is adjustable. The other geometrical parameters of the cooling system like the nozzle diameter or the

  11. High-resolution infrared spectrum of jet-cooled methyl acetate in the C=O stretching region: Internal rotations of two inequivalent methyl tops

    NASA Astrophysics Data System (ADS)

    Sunahori, Fumie X.; Borho, Nicole; Liu, Xunchen; Xu, Yunjie

    2011-12-01

    The jet-cooled high resolution infrared (IR) spectrum of methyl acetate (MA), CH3-C(=O)-O-CH3, in the C=O fundamental band region was recorded by using a rapid scan IR laser spectrometer equipped with an astigmatic multipass cell. No high resolution IR analyses of the ro-vibrational transitions between the ground and non-torsionally excited vibrational states have hitherto been reported for molecules with two inequivalent methyl rotors. Because of the two chemically different methyl tops in MA, i.e., the acetyl -CH3 and methoxy -CH3, each rotational energy level is split into more than two torsional sublevels by internal rotations of these methyl groups. We were able to assign ro-vibrational transitions of four torsional species by using the ground state combination differences calculated from the molecular constants of the vibrational ground state recently determined by a global fit of the microwave and millimeter wave lines [M. Tudorie, I. Kleiner, J. T. Hougen, S. Melandri, L. W. Sutikdja, and W. Stahl, J. Mol. Spectrosc. 269, 211 (2011)]. The assigned lines were successfully fitted using the BELGI-Cs-IR program to an overall standard deviation which is comparable to the measurement accuracy. This study is also of interest in understanding the role of methyl rotors in the intramolecular vibrational-energy redistribution processes in mid-size organic molecules.

  12. High-resolution infrared spectrum of jet-cooled methyl acetate in the C=O stretching region: internal rotations of two inequivalent methyl tops.

    PubMed

    Sunahori, Fumie X; Borho, Nicole; Liu, Xunchen; Xu, Yunjie

    2011-12-21

    The jet-cooled high resolution infrared (IR) spectrum of methyl acetate (MA), CH(3)-C(=O)-O-CH(3), in the C=O fundamental band region was recorded by using a rapid scan IR laser spectrometer equipped with an astigmatic multipass cell. No high resolution IR analyses of the ro-vibrational transitions between the ground and non-torsionally excited vibrational states have hitherto been reported for molecules with two inequivalent methyl rotors. Because of the two chemically different methyl tops in MA, i.e., the acetyl -CH(3) and methoxy -CH(3), each rotational energy level is split into more than two torsional sublevels by internal rotations of these methyl groups. We were able to assign ro-vibrational transitions of four torsional species by using the ground state combination differences calculated from the molecular constants of the vibrational ground state recently determined by a global fit of the microwave and millimeter wave lines [M. Tudorie, I. Kleiner, J. T. Hougen, S. Melandri, L. W. Sutikdja, and W. Stahl, J. Mol. Spectrosc. 269, 211 (2011)]. The assigned lines were successfully fitted using the BELGI-Cs-IR program to an overall standard deviation which is comparable to the measurement accuracy. This study is also of interest in understanding the role of methyl rotors in the intramolecular vibrational-energy redistribution processes in mid-size organic molecules. PMID:22191878

  13. The vibrationless Ã←X˜ transition of the jet-cooled deuterated methyl peroxy radical CD3O2 by cavity ringdown spectroscopy

    NASA Astrophysics Data System (ADS)

    Wu, Shenghai; Dupré, Patrick; Rupper, Patrick; Miller, Terry A.

    2007-12-01

    The nearly rotationally resolved spectrum of the ÃA'2←X˜A″2 000 transition of perdeutero methyl peroxy near 1.35μm has been studied via pulsed cavity ringdown spectroscopy. Albeit, this is a weak transition, it is possible to observe the spectrum under jet-cooled conditions (≈15K) by combining a source of narrow-bandwidth radiation (≈250MHz) with a supersonic slit-jet expansion incorporating an electric discharge. The near infrared radiation was obtained by using stimulated Raman scattering and a pulsed, nearly Fourier-transform-limited Ti:sapphire amplifier seeded by a scanable cw Ti:sapphire ring laser. The experimental spectrum has been fitted using a model Hamiltonian that includes the rigid body rotation of an asymmetric top and the spin-rotation interaction. An excellent quality fit was obtained resulting in the determination of 15molecular parameters characterizing the à and X˜ states. Other results reported for CD3O2 include an estimate of the radical concentration and the vibronic transition dipole from the observed absorption intensities. Details about the spectral linewidths are also discussed.

  14. Note: High density pulsed molecular beam for cold ion chemistry

    SciTech Connect

    Kokish, M. G.; Rajagopal, V.; Marler, J. P.; Odom, B. C.

    2014-08-15

    A recent expansion of cold and ultracold molecule applications has led to renewed focus on molecular species preparation under ultrahigh vacuum conditions. Meanwhile, molecular beams have been used to study gas phase chemical reactions for decades. In this paper, we describe an apparatus that uses pulsed molecular beam technology to achieve high local gas densities, leading to faster reaction rates with cold trapped ions. We characterize the beam's spatial profile using the trapped ions themselves. This apparatus could be used for preparation of molecular species by reactions requiring excitation of trapped ion precursors to states with short lifetimes or for obtaining a high reaction rate with minimal increase of background chamber pressure.

  15. Spectroscopy of Jet-Cooled Neutral and Ionized PAHs: Implications for Interstellar Dust

    NASA Technical Reports Server (NTRS)

    Salama, F.; Tan, X.; Biennier, L.; Cami, J.

    2005-01-01

    We present the gas-phase spectroscopy of neutral and ionized polycyclic aromatic hydrocarbons (PAHs) measured in the W-Visible-NIR range in an astrophysically relevant environment. These measurements provide data on PAHs and nanometer sized particles that can now be directly compared to astronomical observations. The harsh physical conditions of the IS medium - characterized by a low temperature, an absence of collisions and strong VUV radiation fields - are simulated in the laborat'ory by associating a molecular beam with an ionizing discharge to generate a cold plasma expansion. PAH ions are formed from the neutral precursors in an isolated environment at low temperature ($\\sim lOO$-K). The spectra of neutral and ionized PAHs are measured using the high sensitivity methods of cavity ring down spectroscopy (CRDS) and multiplex integrated cavity output spectroscopy (MICOS). These experiments provide unique information on the spectra of free, cold large carbon molecules and ions in the gas phase. The electronic bands measured for ionized PAH are found to be intrinsically broad ($\\geq$20 cm$^{-l}$) while the bands associated with the neutral precursors are narrower (of the order of 2 - 10 cm$^{-l}$). The laboratory data are discussed and compared with recent astronomical spectra of large and narrow DIBs and with the spectra of circumstellar environments of selected carbon stars (see contribution of Cami et al.) and the implications for the interstellar PAH population are derived. Preliminary results also show that carbon nanoparticles are formed during the short residence time of the precursors in the plasma. This finding holds great potential for understanding the formation process of interstellar grains.

  16. Moderate Resolution Jet Cooled Cavity Ringdown Spectra of the tilde{A} State of NO_3 Radical

    NASA Astrophysics Data System (ADS)

    Codd, Terrance J.; Chen, Ming-Wei; Roudjane, Mourad; Miller, Terry A.

    2012-06-01

    The tilde{A}-tilde{X} spectrum of NO_3 has been previously observed using cavity ringdown spectroscopy (CRDS) by Andrei Deev et. al under ambient conditions. There the authors assigned a number of vibronic bands in the spectrum. However, under these conditions, hot-bands may be present and the spectrum becomes very congested at frequencies higher than ˜8700 cm-1 due to the density of vibronic states and the overlap of their rotational contours. In order to obtain more information about the tilde{A} state of NO_3 we recently obtained spectra from 7550 cm-1 to over 10000 cm-1 using our moderate resolution (≃ 0.05 cm-1) jet cooled CRDS apparatus. Jet cooling in our apparatus reduces the rotational temperature to <30 K and eliminates vibrational hot bands greatly simplifying the spectrum. We are able to resolve and assign more than 15 vibronic features including a new assignment of the 31_0 band. Analysis of the ν_4 progression shows weak Jahn-Teller coupling in this mode. Anomalous band contours and anharmonic spacings are observed for the ν_1ν_4 combination bands and the cause is being investigated. We also see some features that could belong to vibronically forbidden transitions which may be magnetic dipole allowed. A. Deev, J. Sommar, and M. Okumura, J. Chem. Phys. 122, 224305 (2005)

  17. Dissociative recombination of molecular ions with electrons

    NASA Technical Reports Server (NTRS)

    Johnsen, Rainer

    1990-01-01

    An overview is presented for the present state of the art of laboratory measurements of the dissociative recombination of molecular ions with electrons. Most work has focussed on obtaining rates and their temperature dependence, as these are of primary interest for model calculations of ionospheres. A comparison of data obtained using the microwave afterglow method, the flowing afterglow technique, and the merged beam technique shows that generally the agreement is quite good, but there are some serious discrepancies, especially in the case of H(3+) recombination, that need to be resolved. Results of some earlier experimental work need to be reexamined in the light of more recent developments. Such cases are pointed out and a compilation of rate coefficients that have withstood scrutiny is presented. Recent advances in experimental methods, such as the use of laser-in-duced fluorescence, make it possible to identify some neutral products of dissociative recombination. What has been done so far and what results one might expect from future work are briefly reviewed.

  18. Performance of water jet cooled silicon monochromators in high power x-ray beams (abstract)

    NASA Astrophysics Data System (ADS)

    Berman, Lonny E.; Hart, Michael

    1992-01-01

    We have fabricated and tested water jet cooled silicon (111) and (220) monochromators specially tailored for extended wiggler beam and concentrated undulator beam power loadings. The tests were made at the X25 27 pole, 1.1 T hybrid wiggler beam line1 at the National Synchrotron Light Source (NSLS). The wiggler-like line-type loading was produced by the direct, unfocused wiggler white beam, in which 300 W of total power in a 60-mm-wide by 5-mm-high [full width at half maximum (FWHM)] cross section were available in the experimental hutch; this represents a typical power density at existing insertion device beam lines. The undulator-like point-type loading was produced by the focused wiggler white beam, generated via reflection of a portion of the direct white beam from a toroidal platinum-coated silicon mirror, resulting in 75 W of total power in a 0.8-mm-wide (FWHM) by 0.45-mm-high (FWHM) cross section in the hutch. This will be a typical power density at next-generation insertion device beam lines. The monochromator design consists of a thin walled silicon box whose bottom is glued to a stainless-steel water manifold; the coolant is delivered through jet tubes directed perpendicular to the underside of the top, diffracting surface of the box.2 Rectangular monochromators with multiple jets were used for the line power loading studies, and cylindrical monochromators with single jets were used for the point power loading studies. Provisions for simple adaptive corrections to compensate for the inevitable beam-induced thermal deformations, consisting of mechanisms to reverse-bend the top surface, and internal heat baffles to frustrate the cooling at the edges of the crystal (to produce an isothermal top surface), were included in the designs. These required approximate matching of the top surface dimensions to the x-ray footprint. To better understand the thermal strain fields, spatial and angular mapping of both fundamental and harmonic Bragg reflections within the

  19. Molecular and negative ion production by a standard electron cyclotron resonance ion source

    SciTech Connect

    Racz, R.; Biri, S.; Juhasz, Z.; Sulik, B.

    2012-02-15

    Molecular and negative ion beams, usually produced in special ion sources, play an increasingly important role in fundamental and applied atomic physics. The ATOMKI-ECRIS is a standard ECR ion source, designed to provide highly charged ion (HCI) plasmas and beams. In the present work, H{sup -}, O{sup -}, OH{sup -}, O{sub 2}{sup -}, C{sup -}, C{sub 60}{sup -} negative ions and H{sub 2}{sup +}, H{sub 3}{sup +}, OH{sup +}, H{sub 2}O{sup +}, H{sub 3}O{sup +}, O{sub 2}{sup +} positive molecular ions were generated in this HCI-ECRIS. Without any major modification in the source and without any commonly applied tricks (such as usage of cesium or magnetic filter), negative ion beams of several {mu}A and positive molecular ion beams in the mA range were successfully obtained.

  20. Molecular Ion Beam Transportation for Low Energy Ion Implantation

    SciTech Connect

    Kulevoy, T. V.; Kropachev, G. N.; Seleznev, D. N.; Yakushin, P. E.; Kuibeda, R. P.; Kozlov, A. V.; Koshelev, V. A.; Hershcovitch, A.; Johnson, B. M.; Gushenets, V. I.; Oks, E. M.; Polozov, S. M.; Poole, H. J.

    2011-01-07

    A joint research and development of steady state intense boron ion sources for 100's of electron-volt ion implanters has been in progress for the past five years. Current density limitation associated with extracting and transporting low energy ion beams result in lower beam currents that in turn adversely affects the process throughput. The transport channel with electrostatic lenses for decaborane (B{sub 10}H{sub 14}) and carborane (C{sub 2}B{sub 10}H{sub 12}) ion beams transportation was developed and investigated. The significant increase of ion beam intensity at the beam transport channel output is demonstrated. The transport channel simulation, construction and experimental results of ion beam transportation are presented.

  1. Precision studies of the hydrogen molecular ion and its isotopologues

    NASA Astrophysics Data System (ADS)

    Bekbayev, A. K.; Aznabayev, D. T.; Korobov, V. I.

    2015-08-01

    We present systematic calculations of the leading order relativistic corrections including the hyperfine splitting (HFS) for a wide range of rotational and vibrational states of the HT+ molecular ion. We also calculate the DC and AC Stark effects for the molecular hydrogen ions and H D + in the non-relativistic approximation. The influence of the DC Stark polarizability effect on the hyperfine substates of a ro-vibrational state is carefully analyzed. Our results enable the detailed evaluation of certain systematic shifts of the transition frequencies for the purpose of ultra-high-precision optical, microwave, or radio-frequency spectroscopy of the hydrogen molecular ions in a trap.

  2. An ion mobility mass spectrometer for investigating photoisomerization and photodissociation of molecular ions

    SciTech Connect

    Adamson, B. D.; Coughlan, N. J. A.; Markworth, P. B.; Bieske, E. J.; Continetti, R. E.

    2014-12-15

    An ion mobility mass spectrometry apparatus for investigating the photoisomerization and photodissociation of electrosprayed molecular ions in the gas phase is described. The device consists of a drift tube mobility spectrometer, with access for a laser beam that intercepts the drifting ion packet either coaxially or transversely, followed by a quadrupole mass filter. An ion gate halfway along the drift region allows the instrument to be used as a tandem ion mobility spectrometer, enabling mobility selection of ions prior to irradiation, with the photoisomer ions being separated over the second half of the drift tube. The utility of the device is illustrated with photoisomerization and photodissociation action spectra of carbocyanine molecular cations. The mobility resolution of the device for singly charged ions is typically 80 and it has a mass range of 100-440 Da, with the lower limit determined by the drive frequency for the ion funnels, and the upper limit by the quadrupole mass filter.

  3. Infrared and Electronic Spectroscopy of the Jet-Cooled 5-Methyl-2-furanylmethyl Radical Derived from the Biofuel 2,5-Dimethylfuran.

    PubMed

    Kidwell, Nathanael M; Mehta-Hurt, Deepali N; Korn, Joseph A; Zwier, Timothy S

    2016-08-18

    The electronic and infrared spectra of the 5-methyl-2-furanylmethyl (MFM) radical have been characterized under jet-cooled conditions in the gas phase. This resonance-stabilized radical is formed by H atom loss from one of the methyl groups of 2,5-dimethylfuran (DMF), a promising second-generation biofuel. As a resonance-stabilized radical, it plays an important role in the flame chemistry of DMF. The D0-D1 transition was studied using two-color resonant two-photon ionization (2C-R2PI) spectroscopy. The electronic origin is in the middle of the visible spectrum (21934 cm(-1) = 455.9 nm) and is accompanied by Franck-Condon activity involving the hindered methyl rotor. The frequencies and intensities are fit to a one-dimensional methyl rotor potential, using the calculated form of the ground state potential. The methyl rotor reports sensitively on the local electronic environment and how it changes with electronic excitation, shifting from a preferred ground state orientation with one CH in-plane and anti to the furan oxygen, to an orientation in the excited state in which one CH group is axial to the plane of the furan ring. Ground and excited state alkyl CH stretch infrared spectra are recorded using resonant ion-dip infrared (RIDIR) spectroscopy, offering a complementary view of the methyl group and its response to electronic excitation. Dramatic changes in the CH stretch transitions with electronic state reflect the changing preference for the methyl group orientation. PMID:27456434

  4. High-resolution absorption spectrum of jet-cooled CH3Cl between 70 000 and 85 000 cm-1: New assignments

    NASA Astrophysics Data System (ADS)

    Cossart-Magos, Claudina; Jungen, Martin; Stalder, Joerg; Launay, Françoise

    2005-09-01

    The absorption spectrum of jet-cooled CH3Cl was photographed from 165to117nm (or 60000-85000cm-1, 7.5-10.5eV) at a resolution limit of 0.0008nm (0.3-0.6cm-1 or 0.04-0.08meV). Even in the best structured region of the spectrum, from 70000to85000cm-1 (8.7-10.5eV ), observed bandwidths (full width at half maximum) are large, from 50to150cm-1. No rotational feature could be resolved. The spectrum is dominated by two strong bands near 9eV, 140nm, the D and E bands of Mulliken [J. Chem. Phys. 8, 382 (1940)] or the spectral region D of Price [J. Chem. Phys.4, 539 (1936)]. Their relative intensity is incompatible with previous assignments, namely, to a triplet and a singlet state belonging to the same configuration. On the basis of the present ab initio calculations, those bands are now assigned to two singlet states, the A11 and E1 excited states resulting from the 2e34pe Rydberg configuration. The present calculations also reveal that the two E1 states issued from 2e34sa1 and 2e34pa1 are quasidegenerate and strongly mixed. They should be assigned to the two broad bands near 8eV, 160nm, the B and C bands of Mulliken and Price. Three vibrational modes are observed to be active: the CCl bond stretch ν3(a1), and the CH3 umbrella and rocking vibrations, respectively, ν2(a1) and ν6(e ). The fundamental frequencies deduced are well within the ranges defined by the corresponding values in the neutral and ion ground states. The possibility of a dynamical Jahn-Teller effect induced by the ν6(e) vibrational mode in the E1 Rydberg states is discussed.

  5. Laser-induced fluorescence, dispersed fluorescence and lifetime measurements of jet-cooled chloro-substituted benzyl radicals

    NASA Astrophysics Data System (ADS)

    Hamatani, Satoshi; Tsuji, Kazuhide; Kawai, Akio; Shibuya, Kazuhiko

    2002-07-01

    We measured the laser-induced fluorescence (LIF) and dispersed fluorescence (DF) spectra of jet-cooled α-, o- and m-chlorobenzyl radicals after they were generated by the 193 nm photolysis of the corresponding parent molecules. The vibronically resolved spectra were obtained to analyze their D1-D0 transitions. The fluorescence lifetimes of α-, o-, m- and p-chlorobenzyls in the zeroth vibrational levels of the D1 states were measured to estimate the oscillator strengths of a series of benzyl derivatives. It was found that the α-substitution is inefficient to break the `accidental forbiddenness' of the D1-D0 transition of benzyl, while the ring-substitution enhances the oscillator strength by 50%.

  6. Molecular ion battery: a rechargeable system without using any elemental ions as a charge carrier

    PubMed Central

    Yao, Masaru; Sano, Hikaru; Ando, Hisanori; Kiyobayashi, Tetsu

    2015-01-01

    Is it possible to exceed the lithium redox potential in electrochemical systems? It seems impossible to exceed the lithium potential because the redox potential of the elemental lithium is the lowest among all the elements, which contributes to the high voltage characteristics of the widely used lithium ion battery. However, it should be possible when we use a molecule-based ion which is not reduced even at the lithium potential in principle. Here we propose a new model system using a molecular electrolyte salt with polymer-based active materials in order to verify whether a molecular ion species serves as a charge carrier. Although the potential of the negative-electrode is not yet lower than that of lithium at present, this study reveals that a molecular ion can work as a charge carrier in a battery and the system is certainly a molecular ion-based “rocking chair” type battery. PMID:26043147

  7. Molecular ion battery: a rechargeable system without using any elemental ions as a charge carrier

    NASA Astrophysics Data System (ADS)

    Yao, Masaru; Sano, Hikaru; Ando, Hisanori; Kiyobayashi, Tetsu

    2015-06-01

    Is it possible to exceed the lithium redox potential in electrochemical systems? It seems impossible to exceed the lithium potential because the redox potential of the elemental lithium is the lowest among all the elements, which contributes to the high voltage characteristics of the widely used lithium ion battery. However, it should be possible when we use a molecule-based ion which is not reduced even at the lithium potential in principle. Here we propose a new model system using a molecular electrolyte salt with polymer-based active materials in order to verify whether a molecular ion species serves as a charge carrier. Although the potential of the negative-electrode is not yet lower than that of lithium at present, this study reveals that a molecular ion can work as a charge carrier in a battery and the system is certainly a molecular ion-based “rocking chair” type battery.

  8. Formation of molecular ions by radiative association of cold trapped atoms and ions

    NASA Astrophysics Data System (ADS)

    Dulieu, Olivier; da Silva, Humberto, Jr.; Aymar, Mireille; Raoult, Maurice

    2015-05-01

    Radiative emission during cold collisions between trapped laser-cooled Rb atoms and alkaline-earth ions (Ca+ , Sr+ , Ba+) and Yb+ are studied theoretically, using accurate effective-core-potential based quantum chemistry calculations of potential energy curves and transition dipole moments of the related molecular ions. Radiative association of molecular ions is predicted to occur for all systems with a cross section two to ten times larger than the radiative charge transfer one. Partial and total rate constants are also calculated and compared to available experiments. Narrow shape resonances are expected, which could be detectable at low temperature with an experimental resolution at the limit of the present standards. Vibrational distributions show that the final molecular ions are not created in their ground state level. Supported by the Marie-Curie ITN ``COMIQ: Cold Molecular Ions at the Quantum limit'' of the EU (#607491).

  9. Expansion Discharge Source for Ion Beam Laser Spectroscopy of Cold Molecular Ions

    NASA Astrophysics Data System (ADS)

    Porambo, Michael; Pearson, Jessica; Riccardo, Craig; McCall, Benjamin J.

    2013-06-01

    Molecular ions are important in several fields of research, and spectroscopy acts as a key tool in the study of these ions. However, problems such as low ion abundance, ion-neutral confusion, and spectral congestion due to high internal temperatures can hinder effective spectroscopic studies. To circumvent these problems, we are developing a technique called Sensitive, Cooled, Resolved, Ion BEam Spectroscopy (SCRIBES). This ion beam spectrometer will feature a continuous supersonic expansion discharge source to produce cold molecular ions, electrostatic ion optics to focus the ions into an ion beam and bend the beam away from co-produced neutral molecules, an overlap region for cavity enhanced spectroscopy, and a time-of-flight mass spectrometer. When completed, SCRIBES will be an effective tool for the study of large, fluxional, and complex molecular ions that are difficult to study with other means. The ion beam spectrometer has been successfully implemented with a hot ion source. This talk will focus on the work of integrating a supersonic expansion discharge source into the instrument. To better understand how the source would work in the whole ion beam instrument, characterization studies are being performed with spectroscopy of HN_2^+ in a section of the system to ascertain the rotational temperature of the ion expansion. Attempts are also underway to measure the ion current from a beam formed from the expansion. Once the source in this environment is properly understood, we will reintegrate it to the rest of the ion beam system, completing SCRIBES. A. A. Mills, B. M. Siller, M. W. Porambo, M. Perera, H. Kreckel and B. J. McCall J. Chem. Phys., 135, 224201, (2011). K. N. Crabtree, C. A. Kauffman and B. J. McCall Rev. Sci. Instrum. 81, 086103, (2010).

  10. Observations of molecular ions in the earth's magnetosphere

    NASA Technical Reports Server (NTRS)

    Craven, P. D.; Chappell, C. R.; Kakani, L.; Olsen, R. C.

    1985-01-01

    The retarding ion mass spectrometer on Dynamics Explorer 1 operating over the polar cap during a large magnetic storm has measured fluxes of up to 10 to the 6th ions/sq cm s of the molecular ions N2(+), NO(+), and O2(+). These ions were measured beginning low in the satellite orbit (1.1 earth radii) and extending to about 3 earth radii geocentric altitude. Near perigee, the ions have a rammed distribution indicating a cold Maxwellian plasma (1000-2000 K). The molecular ions gradually shift to a field-aligned distribution at the higher alitudes. An upward flow of 5-10 km/s is found in these field-aligned measurements. The density of the molecular ions is on the order of 2/cu cm at all altitudes, and the energy of the ions generally increases as the satellite moves sunward across the southern polar cap. Kinetic energies of at least 20 eV were found at 2.5 earth-radii geocentric distance.

  11. Understanding ion association states and molecular dynamics using infrared spectroscopy

    NASA Astrophysics Data System (ADS)

    Masser, Hanqing

    A molecular level understanding of the ion transport mechanism within polymer electrolytes is crucial to the further development for advanced energy storage applications. This can be achieved by the identification and quantitative measurement of different ion species in the system and further relating them to the ion conductivity. In the first part of this thesis, research is presented towards understanding the ion association states (free ions, ion pairs and ion aggregates) in ionomer systems, and the correlation of ion association states, ion conduction, polymer dynamics, and morphology. Ion conductivity in ionomers can be improved by lowering glass transition temperature, increasing polymer ion solvation ability, and adjusting ionomer structural variables such as ion content, cation type and side chain structure. These effects are studied in three ionomer systems respectively, using a combination of characterization methods. Fourier Transform Infrared Spectroscopy (FTIR) identifies and quantifies the ion association states. Dielectric Spectroscopy (DRS) characterizes ion conductivity and polymer and ion dynamics. X-ray scattering reveals changes in morphology. The influence of a cation solvating plasticizer on a polyester ionomer is systematically investigated with respect to ion association states, ion and polymer dynamics and morphology. A decrease in the number ratio of ion aggregates with increased plasticizer content and a slight increase at elevated temperature are observed in FTIR. Similar results are also detected by X-ray scattering. As determined from dielectric spectroscopy, ion conductivity increases with plasticizer content, in accordance with the decrease in glass transition temperature. Research on copolymer of poly(ethylene oxide) (PEO) and poly(tetramethylene oxide) (PTMO) based ionomers further develops an understanding of the trade-off between ion solvation and segmental dynamics. Upon the incorporation of PTMO, the majority of the PTMO

  12. Theoretical Study of Negative Molecular Ions

    NASA Astrophysics Data System (ADS)

    Simons, Jack

    2011-05-01

    Although this review provides references to tabulations of molecular electron affinities, primarily it focuses on explaining why theory plays an important role in understanding the behavior of anions, explaining the challenges that anions pose to theory, making connections between the theories used to compute electron affinities and the potentials (e.g., charge-dipole, charge-quadrupole, valence attraction and exchange repulsion, dispersion, and polarization) that govern the electron-molecule interaction, and discussing how species with negative electron affinities may possess metastable anion states and how such states should be treated. In addition to references to published literature, many links are given to websites of practicing theoretical chemists who study molecular anions; these links (which appear in boldface) offer the reader a broad avenue to access much more information about molecular anions than can be covered in a review or even through conventional literature sources.

  13. Dissociation Dynamics of Molecular Ions in High dc Electric Field.

    PubMed

    Blum, Ivan; Rigutti, Lorenzo; Vurpillot, François; Vella, Angela; Gaillard, Aurore; Deconihout, Bernard

    2016-05-26

    In an atom probe, molecular ions can be field evaporated from the analyzed material and, then, can dissociate under the very intense electric field close to the field emitter. In this work, field evaporation of ZnO reveals the emission of Zn2O2(2+) ions and their dissociation into ZnO(+) ions. It is shown that the repulsion between the produced ZnO(+) ions is large enough to have a measurable effect on both the ion trajectories and times of flight. Comparison with numerical simulations of the ion trajectories gives information on the lifetime of the parent ions, the energy released by the dissociation and repulsion, and also the dissociation direction. This study not only opens the way to a new method to obtain information on the behavior of molecular ions in high electric fields by using an atom probe, but also opens up the interesting perspective to apply this technique to a wide class of materials and molecules. PMID:27136453

  14. Periodic orbits of the hydrogen molecular ion and their quantization

    SciTech Connect

    Duan, Y.; Yuan, J.; Bao, C.

    1995-11-01

    In a classical study of the hydrogen molecular ion beyond the Born-Oppenheimer approximation (BOA), we have found that segments of trajectories resemble that of the Born-Oppenheimer approximation periodic orbits. The importance of this fact to the classical understanding of chemical bonding leads us to a systematic study of the periodic orbits of the planar hydrogen molecular ion within the BOA. Besides introducing a classification scheme for periodic orbits, we discuss the convergence properties of families of periodic orbits and their bifurcation patterns according to their types. Semiclassical calculations of the density of states based on these periodic orbits yield results in agreement with the exact quantum eigenvalues of the hydrogen molecular ion system.

  15. Optical Pulse-Shaping for Internal Cooling of Molecular Ions

    NASA Astrophysics Data System (ADS)

    Lien, Chien-Yu; Williams, Scott R.; Odom, Brian

    2011-06-01

    We propose a scheme to use pulse-shaped femtosecond lasers to optically cool the internal degrees of freedom of molecular ions. Since this approach relies on cooling rotational and vibrational quanta by exciting an electronic transition, it is most straightforward for molecular ions with diagonal Frank-Condon-Factors. The scheme has the advantage of requiring only tens of microseconds to reach equilibrium without blackbody radiation to redistribute the population. For AlH+, a candidate species, a rate equation simulation shows equilibrium is achieved in 15 μs.

  16. Infrared spectra of small molecular ions trapped in solid neon

    SciTech Connect

    Jacox, Marilyn E.

    2015-01-22

    The infrared spectrum of a molecular ion provides a unique signature for that species, gives information on its structure, and is amenable to remote sensing. It also serves as a comparison standard for refining ab initio calculations. Experiments in this laboratory trap molecular ions in dilute solid solution in neon at 4.2 K in sufficient concentration for observation of their infrared spectra between 450 and 4000 cm{sup !1}. Discharge-excited neon atoms produce cations by photoionization and/or Penning ionization of the parent molecule. The resulting electrons are captured by other molecules, yielding anions which provide for overall charge neutrality of the deposit. Recent observations of ions produced from C{sub 2}H{sub 4} and BF{sub 3} will be discussed. Because of their relatively large possibility of having low-lying excited electronic states, small, symmetric molecular cations are especially vulnerable to breakdown of the Born-Oppenheimer approximation. Some phenomena which can result from this breakdown will be discussed. Ion-molecule reaction rates are sufficiently high that in some systems absorptions of dimer cations and anions are also observed. When H{sub 2} is introduced into the system, the initially-formed ion may react with it. Among the species resulting from such ion-molecule reactions that have recently been studied are O{sub 4}{sup +}, NH{sub 4}{sup +}, HOCO{sup +}, and HCO{sub 2}{sup !}.

  17. Infrared spectra of small molecular ions trapped in solid neon

    NASA Astrophysics Data System (ADS)

    Jacox, Marilyn E.

    2015-01-01

    The infrared spectrum of a molecular ion provides a unique signature for that species, gives information on its structure, and is amenable to remote sensing. It also serves as a comparison standard for refining ab initio calculations. Experiments in this laboratory trap molecular ions in dilute solid solution in neon at 4.2 K in sufficient concentration for observation of their infrared spectra between 450 and 4000 cm!1. Discharge-excited neon atoms produce cations by photoionization and/or Penning ionization of the parent molecule. The resulting electrons are captured by other molecules, yielding anions which provide for overall charge neutrality of the deposit. Recent observations of ions produced from C2H4 and BF3 will be discussed. Because of their relatively large possibility of having low-lying excited electronic states, small, symmetric molecular cations are especially vulnerable to breakdown of the Born-Oppenheimer approximation. Some phenomena which can result from this breakdown will be discussed. Ion-molecule reaction rates are sufficiently high that in some systems absorptions of dimer cations and anions are also observed. When H2 is introduced into the system, the initially-formed ion may react with it. Among the species resulting from such ion-molecule reactions that have recently been studied are O4+, NH4+, HOCO+, and HCO2!.

  18. Jet-Cooled ~A-~X Spectra of the β-HYDROXYETHYLPEROXY and β-HYDROXYETHYLPEROXY-OD Radicals

    NASA Astrophysics Data System (ADS)

    Chen, Ming-Wei; Just, Gabriel M. P.; Codd, Terrance; Miller, Terry A.

    2010-06-01

    The β-hydroxyethylperoxy (HOCH_2CH_2OO, β-HEP) radical in the atmosphere arises from the reaction of ethene (CH_2CH_2) and hydroxyl radical (OH), followed by the reaction with oxygen (O_2). It is also an important intermediate in the oxidation of ethanol, a component of automotive fuel. High-resolution, jet-cooled cavity ring-down spectroscopy (resolution of Δν≈250MHz, considering the instrumental linewidth and the residual Doppler broadening) has been applied to observe the ~A-~X origin band of the most stable conformer of both β-HEP and mono-deuterated β-HEP (DOCH_2CH_2OO, β-HEP-OD). Broadened rotational contours are observed for both isotopologues, but more resolved structure is shown in the β-HEP-OD spectrum. The evolutionary algorithm approach is applied to analyze the spectra, which gives fitted rotational constants and the homogeneous linewidths for both isotopologues using an asymmetric-top model for the rotational Hamiltonian. Evidence corresponding to a narrower homogeneous linewidth in the β-HEP-OD spectra implies that the broad rotational contour of β-HEP likely involves the motion of the hydrogen of the OH group.

  19. Ultrafast excited-state H-atom transfer in jet-cooled 2-(2'-hydroxyphenyl)-oxazole derivatives

    NASA Astrophysics Data System (ADS)

    Douhal, A.; Lahmani, F.; Zehnacker-Rentien, A.; Amat-Guerri, F.

    1996-04-01

    The fluorescence excitation and dispersed emission spectra of jet-cooled 2-(2'-hydroxyphenyl)- 4-phenyloxazole (HPPO) and its OH deuterated derivative, DPPO have been investigated. The dispersed fluorescence of both compounds exhibits an identical large Stokes shift. While the excitation spectrum of HPPO is composed of broad overlapping bands, the deuteration of the OH group induces a drastic narrowing of the vibronic structures which are well reproduced by Lorentzian lineshapes corresponding to an homogeneous width ranging from 24 to 30 cm-1 for HPPO and from 3.6 to 9.7 cm-1 for HPPO. The results are interpreted in terms of the occurrence of a fast (≳4.5×1012 s-1) excited-state intramolecular proton-tunnelling-transfer reaction in the enol form producing a keto tautomer through an asymmetric potential energy surface with a small energy barrier. The kinetic isotope effect observed here cannot be described in terms of a monodimensional tunnel effect and may rather involve a multidimensional coordinate involving low frequency motions. 2-(2'-hydroxyphenyl)-4-methyloxazole was also investigated and the influence of complexation on the proton transfer efficiency has been discussed.

  20. Ultrafast excited-state H-atom transfer in jet-cooled 2-(2'-hydroxyphenyl)-oxazole derivatives

    SciTech Connect

    Douhal, A.; Lahmani, F.; Zehnacker-Rentien, A.; Amat-Guerri, F.

    1996-04-01

    The fluorescence excitation and dispersed emission spectra of jet-cooled 2-(2'-hydroxyphenyl)- 4-phenyloxazole (HPPO) and its OH deuterated derivative, DPPO have been investigated. The dispersed fluorescence of both compounds exhibits an identical large Stokes shift. While the excitation spectrum of HPPO is composed of broad overlapping bands, the deuteration of the OH group induces a drastic narrowing of the vibronic structures which are well reproduced by Lorentzian lineshapes corresponding to an homogeneous width ranging from 24 to 30 cm{sup -1} for HPPO and from 3.6 to 9.7 cm{sup -1} for HPPO. The results are interpreted in terms of the occurrence of a fast (> or approx. 4.5x10{sup 12} s{sup -1}) excited-state intramolecular proton-tunnelling-transfer reaction in the enol form producing a keto tautomer through an asymmetric potential energy surface with a small energy barrier. The kinetic isotope effect observed here cannot be described in terms of a monodimensional tunnel effect and may rather involve a multidimensional coordinate involving low frequency motions. 2-(2'-hydroxyphenyl)-4-methyloxazole was also investigated and the influence of complexation on the proton transfer efficiency has been discussed.

  1. High-resolution absorption cross section measurements of supersonic jet-cooled carbon monoxide between 92.5 and 97.4 nanometers

    NASA Technical Reports Server (NTRS)

    Yoshino, K.; Stark, G.; Esmond, J. R.; Smith, P. L.; Ito, K.; Matsui, T.

    1995-01-01

    High-resolution photoabsorption cross sections for eight CO bands, at wavelengths between 92.5 nm and 97.4 nm, have been measured in a supersonic jet-cooled source (approximately equals 20 K) at the Photon Factory synchrotron radiation facility. New integrated cross sections are reported for four bands between 92.5 nm and 94.2 nm. A low-temperature spectrum of the W(1)-X(0) band (95.6 nm), which was used to determine the absorbing CO column densities, is also presented. Additional jet-cooled cross section measurements were made on the L(0)-X(0), K(0)-X(0), and W(0)-X(0) bands (96.7-97.4 nm) which verify previously published results. A self-consistent set of band oscillator strengths is presented for the eight bands studied.

  2. a Novel Method to Measure Spectra of Cold Molecular Ions

    NASA Astrophysics Data System (ADS)

    Chakrabarty, Satrajit; Holz, Mathias; Campbell, Ewen; Banerjee, Agniva; Gerlich, Dieter; Maier, John P.

    2014-06-01

    A universal method has been developed in our group for measuring the spectra of molecular ions in a 22-pole radio frequency trap at low temperatures. It is based on laser induced inhibition of complex growth (LIICG)1. At low temperatures and high number densities of buffer gas, helium attaches to ions via ternary association. The formation of these weakly bound complexes, however, is inhibited following resonant absorption of the bare molecular ion. The first successful measurements have been demonstrated on the A 2Π_u ← X ^2Σ_g^+ electronic transition of N_2^+, with some thousand N_2^+ ions, helium densities of 1015 cm-3, and storage times of 1 s. The reduction in the number of N_2+-He complexes is the result of an interplay between excitation, radiative and collisional cooling, ternary association, and collision induced dissociation, and is explained using a kinetic model. The method is also applicable to larger molecular species. In this case internal conversion following electronic excitation produces internally "hot" ions, reducing the attachment of helium. The technique is universal because complex formation can be impeded over a wide wavelength range. [1] S. Chakrbarty, M. Holz, E. K. Campbell, A. Banerjee, D. Gerlich, and J. P. Maier, J. Phys. Chem. Lett. 2013, 4, 4051.

  3. A Cartoon in One Dimension of the Hydrogen Molecular Ion

    ERIC Educational Resources Information Center

    Dutta, Sourav; Ganguly, Shreemoyee; Dutta-Roy, Binayak

    2008-01-01

    To illustrate the basic methodology involved in the quantum mechanics of molecules, a one-dimensional caricature of the hydrogen molecular ion (H[superscript +][subscript 2]) is presented, which is exactly solvable, in the Born-Oppenheimer approximation, in terms of elementary functions. The purpose of the exercise is to elucidate in a simple…

  4. Utilizing Ion-Mobility Data to Estimate Molecular Masses

    NASA Technical Reports Server (NTRS)

    Duong, Tuan; Kanik, Isik

    2008-01-01

    A method is being developed for utilizing readings of an ion-mobility spectrometer (IMS) to estimate molecular masses of ions that have passed through the spectrometer. The method involves the use of (1) some feature-based descriptors of structures of molecules of interest and (2) reduced ion mobilities calculated from IMS readings as inputs to (3) a neural network. This development is part of a larger effort to enable the use of IMSs as relatively inexpensive, robust, lightweight instruments to identify, via molecular masses, individual compounds or groups of compounds (especially organic compounds) that may be present in specific environments or samples. Potential applications include detection of organic molecules as signs of life on remote planets, modeling and detection of biochemicals of interest in the pharmaceutical and agricultural industries, and detection of chemical and biological hazards in industrial, homeland-security, and industrial settings.

  5. Spectroscopy of Benzyl-Type Radicals Generated by Electric Discharge : Jet-Cooled Dichlorobenzyl Radicals

    NASA Astrophysics Data System (ADS)

    Yoon, Young Wook; Lee, Sang Kuk

    2013-06-01

    The technique of corona excited supersonic expansion coupled with a pinhole-type glass nozzle has been proved a useful laser-free spectroscopic tool for observation of vibronic emission spectra of large aromatic molecules, especially for molecular radicals which are long believed to play an important role as a reaction intermediate in aromatic chemical reactions. The vibronic emission spectra recorded with a long-path monochromator exhibit the electronic transition energy in the D_1 → D_0 transition and vibrational mode frequencies at the D_0 state. In this laboratory, all six isomeric dichlorobenzyl radicals have been produced from the corona discharge of corresponding dichlorotoluenes seeded in a large amount of inert carrier gas He. The vibronic emission spectra show very weak intensity due to the existence of Cl atoms in the precursor molecules and possible breakdown of benzene ring by free Cl atoms. Nevertheless, we clearly identified the origin band and a few well-known vibrational modes for each isomer. From an analysis of the spectra observed, we determined the energy of electronic transition and several vibrational modes in the ground electronic state. Also, the red-shift of the origin band from the parental benzyl radical clearly shows the substituent effect of Cl atoms on electronic energy, for which we satisfactorily explain in terms of the shape of the molecular planes and position of the nodal points at a given electronic state, recently developed in this laboratory for identification of isomeric multi-substituted benzyl-type radicals. Y. W. Yoon, C. S. Huh, and S. K. Lee, Chem. Phys. Lett. {550}, 58 (2012). S. K. Lee and S. J. Kim, Chem. Phys. Lett. {412}, 88 (2005).

  6. Foil dissociation of fast molecular ions into atomic excited states

    SciTech Connect

    Berry, H.G.; Gay, T.J.; Brooks, R.L.

    1980-01-01

    The intensity and polarizations of light emitted from atomic excited states of dissociated molecular ions were measured. The dissociations are induced when fast molecular ions (50 to 500 keV/amu) are transmitted through thin carbon foils. A calculation of multiple scattering and the Coulomb explosion gives the average internuclear separation of the projectile at the foil surface. Experimentally, the foil thickness is varied to give varying internuclear separations at the foil surface and observe the consequent variation in light yield and optical polarization. Using HeH/sup +/ projectiles, factors of 1 to 5 enhancements of the light yields from n = 3, /sup 1/ /sup 3/P,D states of He I and some He II and H I emissions were observed. The results can be explained in terms of molecular level crossings which provide mixings of the various final states during dissociation of the molecular ions at the exit surface. They suggest a short range surface interaction of the electron pick-up followed by a slow molecular dissociation. Alignment measurements confirm the essential features of the model. Observations of Lyman ..cap alpha.. emission after dissociation of H/sub 2//sup +/ amd H/sub 3//sup +/ show rapid variations in light yield for small internuclear separations at the foil surface.

  7. Candidate molecular ions for an electron electric dipole moment experiment

    SciTech Connect

    Meyer, Edmund R.; Bohn, John L.; Deskevich, Michael P.

    2006-06-15

    This paper is a theoretical work in support of a newly proposed experiment [R. Stutz and E. Cornell, Bull. Am. Soc. Phys. 89, 76 (2004)] that promises greater sensitivity to measurements of the electron's electric dipole moment (EDM) based on the trapping of molecular ions. Such an experiment requires the choice of a suitable molecule that is both experimentally feasible and possesses an expectation of a reasonable EDM signal. We find that the molecular ions PtH{sup +} and HfH{sup +} are both suitable candidates in their low-lying {sup 3}{delta} states. In particular, we anticipate that the effective electric fields generated inside these molecules are approximately 73 and -17 GV/cm, respectively. As a byproduct of this discussion, we also explain how to make estimates of the size of the effective electric field acting in a molecule, using commercially available nonrelativistic molecular structure software.

  8. Spectroscopy and Dynamics of Jet-Cooled Polyynes in a Slit Supersonic Discharge: Sub-Doppler Infrared Studies of Diacetylene HCCCCH.

    PubMed

    Chang, Chih-Hsuan; Nesbitt, David J

    2015-07-16

    Fundamental, bending (ν6, ν7, ν8, ν9), and CC-stretch (ν2, ν3) hot band spectra in the antisymmetric CH stretch (ν4) region near 3330 cm(-1) have been observed and analyzed for jet cooled diacetylene (HC≡C-C≡CH) under sub-Doppler conditions. Diacetylene is generated in situ in the throat of a pulsed supersonic slit expansion by discharge dissociation of acetylene to form ethynyl (C≡CH) + H, followed by radical attack (HC≡CH + C≡C-H) to form HC≡C-C≡CH + H. The combination of (i) sub-Doppler line widths and (ii) absence of spectral congestion permits rotational structure and Coriolis interactions in the ν4 CH stretch fundamental to be observed and analyzed with improved precision. Of particular dynamical interest, the spectra reveal diacteylene formation in highly excited internal vibrational states. Specifically, multiple Π ← Π and Δ ← Δ hot bands built on the ν4 CH stretch fundamental are observed, due to doubly degenerate bending vibrations [cis C≡C-H bend (ν6), trans C-C≡C bend (ν7), trans C≡C-H bend (ν8) and cis C-C≡C bend (ν9)], as well as a heretofore unobserved Σ ← Σ band assigned to excitation of ν2 or 2ν3 CC stretch. Boltzmann analysis yields populations consistent with universally cold rotations (Trot ≈ 15 ± 5 K) and yet superthermal vibrations (Tvib ≈ 85-430 K), the latter of which is quite anomalous for the high collision densities in a slit jet expansion. In order to elucidate the physical mechanism for this excess vibrational excitation, high level ab initio CCSD(T) calculations have been pursued with explicitly correlated basis sets (VnZ-f12; n = 2,3) and extrapolated to the complete basis set (CBS) limit using MOLPRO quantum chemistry software. The results suggest that the extensive hot band structure observed arises from (i) highly exothermic CCH + HCCH addition to yield a strongly bent HCCHCCH radical intermediate (ΔH = -62.6 kcal/mol), followed by (ii) rapid fragmentation over a submerged

  9. An experimental and ab initio study of the electronic spectrum of the jet-cooled F{sub 2}BO free radical

    SciTech Connect

    Grimminger, Robert; Clouthier, Dennis J.; Sheridan, Phillip M.

    2014-04-28

    We have studied the B{sup ~} {sup 2}A{sub 1}–X{sup ~} {sup 2}B{sub 2} laser-induced fluorescence (LIF) spectrum of the jet-cooled F{sub 2}BO radical for the first time. The transition consists of a strong 0{sub 0}{sup 0} band at 446.5 nm and eight weak sequence bands to shorter wavelengths. Single vibronic level emission spectra obtained by laser excitation of individual levels of the B{sup ~} state exhibit two electronic transitions: a very weak, sparse B{sup ~}–X{sup ~} band system in the 450–500 nm region and a stronger, more extensive set of B{sup ~} {sup 2}A{sub 1}–A{sup ~} {sup 2}B{sub 1} bands in the 580–650 nm region. We have also performed a series of high level ab initio calculations to predict the electronic energies, molecular structures, vibrational frequencies, and rotational and spin-rotation constants in the X{sup ~} {sup 2}B{sub 2}, A{sup ~2}B{sub 1} and B{sup ~} {sup 2}A{sub 1} electronic states as an aid to the analysis of the experimental data. The theoretical results have been used as input for simulations of the rotationally resolved B{sup ~} {sup 2}A{sub 1}–X{sup ~} {sup 2}B{sub 2} 0{sub 0}{sup 0} LIF band and Franck-Condon profiles of the LIF and single vibronic level emission spectra. The agreement between the simulations obtained with purely ab initio parameters and the experimental spectra validates the geometries calculated for the ground and excited states and the conclusion that the radical has C{sub 2v} symmetry in the X{sup ~}, A{sup ~}, and B{sup ~} states. The spectra provide considerable new information about the vibrational energy levels of the X{sup ~} and A{sup ~} states, but very little for the B{sup ~} state, due to the very restrictive Franck-Condon factors in the LIF spectra.

  10. Behavior of molecules and molecular ions near a field emitter

    NASA Astrophysics Data System (ADS)

    Gault, Baptiste; Saxey, David W.; Ashton, Michael W.; Sinnott, Susan B.; Chiaramonti, Ann N.; Moody, Michael P.; Schreiber, Daniel K.

    2016-03-01

    The cold emission of particles from surfaces under intense electric fields is a process which underpins a variety of applications including atom probe tomography (APT), an analytical microscopy technique with near-atomic spatial resolution. Increasingly relying on fast laser pulsing to trigger the emission, APT experiments often incorporate the detection of molecular ions emitted from the specimen, in particular from covalently or ionically bonded materials. Notably, it has been proposed that neutral molecules can also be emitted during this process. However, this remains a contentious issue. To investigate the validity of this hypothesis, a careful review of the literature is combined with the development of new methods to treat experimental APT data, the modeling of ion trajectories, and the application of density-functional theory simulations to derive molecular ion energetics. It is shown that the direct thermal emission of neutral molecules is extremely unlikely. However, neutrals can still be formed in the course of an APT experiment by dissociation of metastable molecular ions. This work is a partial contribution of the US Government and therefore is not subject to copyright in the United States.

  11. Gas feeding molecular phosphorous ion source for semiconductor implanters.

    PubMed

    Gushenets, V I; Oks, E M; Bugaev, A S; Kulevoy, T V; Hershcovitch, A

    2014-02-01

    Phosphorus is a much used dopant in semiconductor technology. Its vapors represent a rather stable tetratomic molecular compound and are produced from one of the most thermodynamically stable allotropic forms of phosphorus-red phosphorus. At vacuum heating temperatures ranging from 325 °C, red phosphorus evaporates solely as P4 molecules (P4/P2 ∼ 2 × 10(5), P4/P ∼ 10(21)). It is for this reason that red phosphorus is best suited as a source of polyatomic molecular ion beams. The paper reports on experimental research in the generation of polyatomic phosphorus ion beams with an alternative P vapor source for which a gaseous compound of phosphorus with hydrogen - phosphine - is used. The ion source is equipped with a specially designed dissociator in which phosphine heated to temperatures close to 700 °C decomposes into molecular hydrogen and phosphorus (P4) and then the reaction products are delivered through a vapor line to the discharge chamber. Experimental data are presented reflecting the influence of the discharge parameters and temperature of the dissociator heater on the mass-charge state of the ion beam. PMID:24593641

  12. Molecular imaging of biological tissue using gas cluster ions

    PubMed Central

    Tian, Hua; Wucher, Andreas; Winograd, Nicholas

    2015-01-01

    An Arn+ (n = 1–6000) gas cluster ion source has been utilized to map the chemical distribution of lipids in a mouse brain tissue section. We also show that the signal from high mass species can be further enhanced by doping a small amount of CH4 into the Ar cluster to enhance the ionization of several biologically important molecules. Coupled with secondary ion mass spectrometry instrumentation which utilizes a continuous Ar cluster ion projectile, maximum spatial resolution and maximum mass resolution can be achieved at the same time. With this arrangement, it is possible to achieve chemically resolved molecular ion images at the 4-µm resolution level. The focused Arn+/[Arx(CH4)y]+ beams (4–10 µm) have been applied to the study of untreated mouse brain tissue. A high signal level of molecular ions and salt adducts, mainly from various phosphocholine lipids, has been seen and directly used to map the chemical distribution. The signal intensity obtained using the pure Ar cluster source, the CH4-doped cluster source and C60 is also presented. PMID:26207076

  13. The molecular dynamics simulation of ion-induced ripple growth

    SciTech Connect

    Suele, P.; Heinig, K.-H.

    2009-11-28

    The wavelength-dependence of ion-sputtering induced growth of repetitive nanostructures, such as ripples has been studied by molecular dynamics (MD) simulations in Si. The early stage of the ion erosion driven development of ripples has been simulated on prepatterned Si stripes with a wavy surface. The time evolution of the height function and amplitude of the sinusoidal surface profile has been followed by simulated ion-sputtering. According to Bradley-Harper (BH) theory, we expect correlation between the wavelength of ripples and the stability of them. However, we find that in the small ripple wavelength ({lambda}) regime BH theory fails to reproduce the results obtained by molecular dynamics. We find that at short wavelengths ({lambda}<35 nm) the adatom yield drops hence no surface diffusion takes place which is sufficient for ripple growth. The MD simulations predict that the growth of ripples with {lambda}>35 nm is stabilized in accordance with the available experimental results. According to the simulations, few hundreds of ion impacts in {lambda} long and few nanometers wide Si ripples are sufficient for reaching saturation in surface growth for for {lambda}>35 nm ripples. In another words, ripples in the long wavelength limit seems to be stable against ion-sputtering. A qualitative comparison of our simulation results with recent experimental data on nanopatterning under irradiation is attempted.

  14. Jet-Cooled Laser Spectroscopy of a Jahn-Teller and Pseudo Jahn-Teller Active Molecule: the Nitrate Radical

    NASA Astrophysics Data System (ADS)

    Chen, Ming-Wei; Takematsu, Kana; Okumura, Mitchio; Miller, Terry A.

    2009-06-01

    Well-known as an important intermediate in atmospheric chemistry, the nitrate radical (NO_3) has been extensively studied both experimentally and theoretically. The three energetically lowest electronic states (tilde{X} ^{2}A_{2}^', tilde{A} ^{2}E^'', and tilde{B} ^{2}E^') are strongly coupled by vibronic interactions and hence it is a textbook molecule for understanding the coupling between nearby potential energy surfaces. Such coupling has been treated in considerable detail theoretically. However, corresponding experimental characterization of the interaction is much less detailed. The experimental results primarily consist of IR measurements of vibrational transitions in the ground state. In addition, the electronically forbidden tilde{A}-tilde{X} transition has been observed in ambient temperature CRDS studies. To understand both the Jahn-Teller and pseudo Jahn-Teller coupling in the molecule, further measurements are required with different selection rules and/or higher resolution to resolve the rotational structures of different transitions. In our group, a high-resolution (source Δν≈ 100 MHz in NIR region), jet-cooled CRDS system can be applied to rotationally resolve the electronically forbidden tilde{A}-tilde{X} transition. Furthermore, our high-resolution LIF/SEP system (source Δν≈ 100 MHz) can provide the direct, rotationally resolved measurements of the tilde{B}-tilde{X} and tilde{B}-tilde{A} transitions by operating in the LIF and SEP modes respectively. Such data can provide unambiguous spectral assignments in the tilde{X}, tilde{A} and tilde{B} states. J. F. Stanton, J. Chem. Phys., 126, 134309 (2007) K. Kawaguchi, E. Hirota, T. Ishiwata, and I. Tanaka, J. Chem. Phys., 93, 951 (1990) K. Kawaguchi, T. Ishiwata, E. Hirota, and I. Tanaka, Chem. Phys., 231, 193 (1998) A. Deev, J. Sommar, and M. Okumura, J. Chem. Phys., 122, 224305 (2005) S. Wu, P. Dupré, and T. A. Miller, Phys. Chem. Chem. Phys., 8, 1682, (2006)

  15. Ion-Pair States in Triplet Molecular Hydrogen

    NASA Astrophysics Data System (ADS)

    Setzer, W.; Baker, B. C.; Ashman, S.; Morgan, T. J.

    2016-05-01

    An experimental search is underway to observe the long range triplet ionic states H+ H- of molecular hydrogen. Resonantly enhanced multi-photon ionization of the metastable c 3∏u- 2 pπ state is used access to the R(1)nd1 n = 21 Rydberg state that serves as an intermediate stepping stone state to probe the energy region above the ionization limit with a second tunable laser photon. The metastable state is prepared by electron capture of 6 keV H2+ions in potassium in a molecular beam. Formation of the H+ H- triplet configuration involves triplet excited states of the H- ion, especially the 2p23Pe state, the second bound state of H- predicted to exist with a lifetime long compared to typical auto ionization lifetimes but not yet observed experimentally. Details of the experiment and preliminary results to date will be presented at the conference.

  16. A controllable molecular sieve for Na+ and K+ ions.

    PubMed

    Gong, Xiaojing; Li, Jichen; Xu, Ke; Wang, Jianfeng; Yang, Hui

    2010-02-17

    The selective rate of specific ion transport across nanoporous material is critical to biological and nanofluidic systems. Molecular sieves for ions can be achieved by steric and electrical effects. However, the radii of Na(+) and K(+) are quite similar; they both carry a positive charge, making them difficult to separate. Biological ionic channels contain precisely arranged arrays of amino acids that can efficiently recognize and guide the passage of K(+) or Na(+) across the cell membrane. However, the design of inorganic channels with novel recognition mechanisms that control the ionic selectivity remains a challenge. We present here a design for a controllable ion-selective nanopore (molecular sieve) based on a single-walled carbon nanotube with specially arranged carbonyl oxygen atoms modified inside the nanopore, which was inspired by the structure of potassium channels in membrane spanning proteins (e.g., KcsA). Our molecular dynamics simulations show that the remarkable selectivity is attributed to the hydration structure of Na(+) or K(+) confined in the nanochannels, which can be precisely tuned by different patterns of the carbonyl oxygen atoms. The results also suggest that a confined environment plays a dominant role in the selectivity process. These studies provide a better understanding of the mechanism of ionic selectivity in the KcsA channel and possible technical applications in nanotechnology and biotechnology, including serving as a laboratory-in-nanotube for special chemical interactions and as a high-efficiency nanodevice for purification or desalination of sea and brackish water. PMID:20102186

  17. Atomic and molecular effects on spherically convergent ion flow. II. Multiple molecular species

    NASA Astrophysics Data System (ADS)

    Emmert, Gilbert A.; Santarius, John F.

    2010-01-01

    A theoretical model for the effect of molecular interactions on the flow of molecular ions in spherically convergent geometry where the inner grid (cathode) is at a large negative potential and the outer grid (anode) is grounded has been developed. The model assumes a weakly ionized deuterium plasma composed of D+, D2+, and D3+ ions that interact with the dominant background gas (D2). The interactions included are charge exchange, ionization, and dissociative processes. The formalism developed includes the bouncing motion of the ions in the electrostatic well and sums over all generations of subsequent ions produced by atomic and molecular processes. This leads to a set of two coupled Volterra integral equations, which are solved numerically. From the solution of the Volterra equations, one can obtain quantities of interest, such as the energy spectra of the ions and fast neutral atoms and molecules, and the fusion reaction rate. To provide an experimental test, the model is applied to inertial electrostatic devices and the calculated neutron production rate is compared to previously reported measurements for one University of Wisconsin inertial electrostatic confinement device [D. C. Donovan et al., Fusion Sci. Technol. 56, 507 (2009)]. The results show general agreement with the experimental results, but significant differences remain to be resolved.

  18. Free ion yields in liquids: Molecular structure and track effects

    SciTech Connect

    Holroyd, R.

    1992-05-01

    The signal generated in a liquid-filled ionization chamber is proporational to the ions that escape, the free ion yield or, G{sub fi}. Recent results show how molecular structure, rate of energy loss (dE/dx) and pressure affect G{sub fi} and give further insight into the ionization process in liquids. As a consequence of the passage of high energy charged particles through a liquid, molecules are ionized and excited. The electrons have kinetic energy initially which allow them to travel some distance away from their geminate cations. The electrons may lose energy to vibrational modes but a significant fraction of the separation occurs while the electrons have subvibrational (near thermal) energy. When the electron finally thermalizes it is within the coulombic field of its parent cation and the two ions constitute a geminate pair. The free ion yield is determined by the fraction of geminate pairs which separate to form free ions as against those that recombine to form excited states.

  19. Free ion yields in liquids: Molecular structure and track effects

    SciTech Connect

    Holroyd, R.

    1992-01-01

    The signal generated in a liquid-filled ionization chamber is proporational to the ions that escape, the free ion yield or, G{sub fi}. Recent results show how molecular structure, rate of energy loss (dE/dx) and pressure affect G{sub fi} and give further insight into the ionization process in liquids. As a consequence of the passage of high energy charged particles through a liquid, molecules are ionized and excited. The electrons have kinetic energy initially which allow them to travel some distance away from their geminate cations. The electrons may lose energy to vibrational modes but a significant fraction of the separation occurs while the electrons have subvibrational (near thermal) energy. When the electron finally thermalizes it is within the coulombic field of its parent cation and the two ions constitute a geminate pair. The free ion yield is determined by the fraction of geminate pairs which separate to form free ions as against those that recombine to form excited states.

  20. Analyzing ion distributions around DNA: sequence-dependence of potassium ion distributions from microsecond molecular dynamics

    PubMed Central

    Pasi, Marco; Maddocks, John H.; Lavery, Richard

    2015-01-01

    Microsecond molecular dynamics simulations of B-DNA oligomers carried out in an aqueous environment with a physiological salt concentration enable us to perform a detailed analysis of how potassium ions interact with the double helix. The oligomers studied contain all 136 distinct tetranucleotides and we are thus able to make a comprehensive analysis of base sequence effects. Using a recently developed curvilinear helicoidal coordinate method we are able to analyze the details of ion populations and densities within the major and minor grooves and in the space surrounding DNA. The results show higher ion populations than have typically been observed in earlier studies and sequence effects that go beyond the nature of individual base pairs or base pair steps. We also show that, in some special cases, ion distributions converge very slowly and, on a microsecond timescale, do not reflect the symmetry of the corresponding base sequence. PMID:25662221

  1. High Resolution Infrared Spectra of Jet-Cooled Formamide and Formamide Dimer in the C=O Stretch Region

    NASA Astrophysics Data System (ADS)

    Sunahori, Fumie X.; Xu, Yunjie

    2012-06-01

    Formamide (FA) is the simplest molecule with a peptide bond. It has attracted considerable theoretical and spectroscopic attention as a model peptide. The structure of the FA monomer in the ground state was determined to be planar by rotational spectral analyses of several isotopic species. Its high resolution FIR spectrum and IR spectrum in the symmetric N-H stretching region were reported previously. Both matrix isolation and jet-cooled FTIR studies of FA dimer reported spectral evidence for the cyclic C2h symmetric FA dimer bonded by two NH---O bonds, which was predicted to be the most stable structure by ab initio calculations. No high-resolution spectrum of FA dimer, however, has been recorded so far. Our aim in the present study is to study high-resolution IR absorption spectra of both FA and its dimer in the C=O stretching region in order to gain information about the peptide-peptide interactions. IR spectrum of the FA monomer was measured using a rapid scan infrared laser spectrometer equipped with an astigmatic multipass cell. While the monomer band centers at 1754 cm-1, the lines most likely belonging to FA dimer were observed around 1740 cm-1. The spectral assignment of the C=O stretching band of the monomer was made by the means of ground state combination differences. Further data collection and spectral analysis of FA dimer are currently underway. The results will be updated at the conference. E. Hirota, R. Sugisaki, C. J. Nielsen, G. O. Sørensen, J. Mol. Spectrosc. 49, 251, 1974. C. L. Brummel, M. Shen, K. B. Hewett, L. A. Philips, J. Opt. Soc. Am. B, 11, 176, 1994 D. McNaughton, C. J. Evans, S. Lane, C. J. Nielsen, J. Mol. Spectrosc., 193, 104, 1999. A. Mardyukov, E. Sanchez-Garcia, P. Rodziewicz, N. L. Doltsinis, W. Sander, J. Phys. Chem. A., 111, 10552, 2007. M. Albrecht, C. A. Rice, M. A. Suhm, J. Phys. Chem. A., 112, 7530, 2008.

  2. Evidence for ion transport and molecular ion dominance in the Venus ionotail

    NASA Technical Reports Server (NTRS)

    Intriligator, D. S.; Brace, L. H.; Cloutier, P. A.; Grebowsky, J. M.; Hartle, R. E.; Kasprzak, W. T.; Knudsen, W. C.; Strangeway, R. J.

    1994-01-01

    We present analyses from the five Pioneer Venus Orbiter plasma experiments and the plasma wave experiment when a patch of plasma with enhanced densities was encountered in the near-Venus ionotail during atmospheric entry at an altitude of approximately 1100 km in the nightside ionosphere. Our analyses of the thermal and superthermal ion measurements in this plasma feature provides the first evidence that at times molecular ions in the 28-32 amu mass range are dominant over atomic mass species thus yielding evidence for a transport mechanism that reaches into the lower ionosphere. Analysis of plasma analyzer (OPA) observations at this time indicates the presence of ions measured in the rest frame of the spacecraft at approximately 27 and 37 volt energy per unit charge steps. In the rest frame of the planet these superthermal ions are flowing from the dawn direction at speeds (assuming they are O2(+)) of approximately 8 km/s and with a flow component downward (perpendicular to the ecliptic plane) at speeds of approximately 2 km/s. OPA analyses also determine the ion number flux, energy, flow angles, and angular distributions. Plasma wave bursts appear to indicate that plasma density decreases within and on the equatorward edge of the patch of enhanced plasma densities are associated with ion acoustic waves and relative ion streaming.

  3. Resonance Enhanced Multi-Photon Ionization and Uv-Uv Hole-Burning Spectroscopic Studies of Jet-Cooled Acetanilide Derivatives

    NASA Astrophysics Data System (ADS)

    Moon, Ceol Joo; Min, Ahreum; Ahn, Ahreum; Lee, Seung Jun; Choi, Myong Yong; Kim, Seong Keun

    2013-06-01

    Conformational investigations and photochemistry of jet-cooled methacetine (MA) and phenacetine (PA) using one color resonant two-photon ionization (REMPI), UV-UV hole-burning and IR-dip spectroscopy are presented. MA and PA are derivatives of acetanilide, substituted by methoxyl, ethoxyl group in the para position of acetanilide, respectively. Moreover, we have investigated conformational information of the acetanilide derivatives (AAP, MA and PA)-water. In this work, we will present and discuss the solvent effects of the hydroxyl group of acetanilide derivatives in the excited state.

  4. Cryogenic molecular separation system for radioactive 11C ion acceleration

    NASA Astrophysics Data System (ADS)

    Katagiri, K.; Noda, A.; Suzuki, K.; Nagatsu, K.; Boytsov, A. Yu.; Donets, D. E.; Donets, E. D.; Donets, E. E.; Ramzdorf, A. Yu.; Nakao, M.; Hojo, S.; Wakui, T.; Noda, K.

    2015-12-01

    A 11C molecular production/separation system (CMPS) has been developed as part of an isotope separation on line system for simultaneous positron emission tomography imaging and heavy-ion cancer therapy using radioactive 11C ion beams. In the ISOL system, 11CH4 molecules will be produced by proton irradiation and separated from residual air impurities and impurities produced during the irradiation. The CMPS includes two cryogenic traps to separate specific molecules selectively from impurities by using vapor pressure differences among the molecular species. To investigate the fundamental performance of the CMPS, we performed separation experiments with non-radioactive 12CH4 gases, which can simulate the chemical characteristics of 11CH4 gases. We investigated the separation of CH4 molecules from impurities, which will be present as residual gases and are expected to be difficult to separate because the vapor pressure of air molecules is close to that of CH4. We determined the collection/separation efficiencies of the CMPS for various amounts of air impurities and found desirable operating conditions for the CMPS to be used as a molecular separation device in our ISOL system.

  5. Molecular Dynamics Simulations of Ion Equilibration in Ultracold Neutral Plasmas

    NASA Astrophysics Data System (ADS)

    Maksimovic, Nikola; Langin, Thomas; Strickler, Trevor; Killian, Thomas

    2015-11-01

    Understanding transport and equilibration in strongly coupled plasmas is important for modeling plasmas found in extreme environments like inertial confinement fusion plasmas and interiors of gas-giant planets. We use molecular dynamics simulations of Yukawa one component plasmas under periodic boundary conditions to study the evolution of strongly coupled ultracold neutral plasmas (UNPs) at early times. Simulations provide access to observable quantities in strongly coupled plasmas, namely correlation functions. Experimentally, the average velocity of an ion subset with a skewed velocity profile has been used to measure velocity autocorrelation functions and provide access to diffusion coefficients and other transport processes in UNPs. Using the simulation, we verify the experimental measurements of average velocities of ion subsets in UNPs and confirm their agreement with the velocity autocorrelation function. Finally, we examine the collective mode behavior of the ions during their equilibration phase by calculating the longitudinal current correlation function at various times during equilibration. This allows us to study the collective mode coupling behavior of the equilibration of ions in UNPs and its dependence on screening parameter.

  6. Deep-UV biological imaging by lanthanide ion molecular protection.

    PubMed

    Kumamoto, Yasuaki; Fujita, Katsumasa; Smith, Nicholas Isaac; Kawata, Satoshi

    2016-01-01

    Deep-UV (DUV) light is a sensitive probe for biological molecules such as nucleobases and aromatic amino acids due to specific absorption. However, the use of DUV light for imaging is limited because DUV can destroy or denature target molecules in a sample. Here we show that trivalent ions in the lanthanide group can suppress molecular photodegradation under DUV exposure, enabling a high signal-to-noise ratio and repetitive DUV imaging of nucleobases in cells. Underlying mechanisms of the photodegradation suppression can be excitation relaxation of the DUV-absorptive molecules due to energy transfer to the lanthanide ions, and/or avoiding ionization and reactions with surrounding molecules, including generation of reactive oxygen species, which can modify molecules that are otherwise transparent to DUV light. This approach, directly removing excited energy at the fundamental origin of cellular photodegradation, indicates an important first step towards the practical use of DUV imaging in a variety of biological applications. PMID:26819825

  7. Deep-UV biological imaging by lanthanide ion molecular protection

    PubMed Central

    Kumamoto, Yasuaki; Fujita, Katsumasa; Smith, Nicholas Isaac; Kawata, Satoshi

    2015-01-01

    Deep-UV (DUV) light is a sensitive probe for biological molecules such as nucleobases and aromatic amino acids due to specific absorption. However, the use of DUV light for imaging is limited because DUV can destroy or denature target molecules in a sample. Here we show that trivalent ions in the lanthanide group can suppress molecular photodegradation under DUV exposure, enabling a high signal-to-noise ratio and repetitive DUV imaging of nucleobases in cells. Underlying mechanisms of the photodegradation suppression can be excitation relaxation of the DUV-absorptive molecules due to energy transfer to the lanthanide ions, and/or avoiding ionization and reactions with surrounding molecules, including generation of reactive oxygen species, which can modify molecules that are otherwise transparent to DUV light. This approach, directly removing excited energy at the fundamental origin of cellular photodegradation, indicates an important first step towards the practical use of DUV imaging in a variety of biological applications. PMID:26819825

  8. Molecular candidates for cardiac stretch-activated ion channels

    PubMed Central

    Reed, Alistair; Kohl, Peter; Peyronnet, Rémi

    2014-01-01

    The heart is a mechanically-active organ that dynamically senses its own mechanical environment. This environment is constantly changing, on a beat-by-beat basis, with additional modulation by respiratory activity and changes in posture or physical activity, and further overlaid with more slowly occurring physiological (e.g. pregnancy, endurance training) or pathological challenges (e.g. pressure or volume overload). Far from being a simple pump, the heart detects changes in mechanical demand and adjusts its performance accordingly, both via heart rate and stroke volume alteration. Many of the underlying regulatory processes are encoded intracardially, and are thus maintained even in heart transplant recipients. Over the last three decades, molecular substrates of cardiac mechanosensitivity have gained increasing recognition in the scientific and clinical communities. Nonetheless, the processes underlying this phenomenon are still poorly understood. Stretch-activated ion channels (SAC) have been identified as one contributor to mechanosensitive autoregulation of the heartbeat. They also appear to play important roles in the development of cardiac pathologies – most notably stretch-induced arrhythmias. As recently discovered, some established cardiac drugs act, in part at least, via mechanotransduction pathways suggesting SAC as potential therapeutic targets. Clearly, identification of the molecular substrate of cardiac SAC is of clinical importance and a number of candidate proteins have been identified. At the same time, experimental studies have revealed variable–and at times contrasting–results regarding their function. Further complication arises from the fact that many ion channels that are not classically defined as SAC, including voltage and ligand-gated ion channels, can respond to mechanical stimulation. Here, we summarise what is known about the molecular substrate of the main candidates for cardiac SAC, before identifying potential further

  9. Imaging ion and molecular transport at subcellular resolution by secondary ion mass spectrometry

    NASA Astrophysics Data System (ADS)

    Chandra, Subhash; Morrison, George H.

    1995-05-01

    The transport of K+, Na+, and Ca2+ were imaged in individual cells with a Cameca IMS-3f ion microscope. Strict cryogenic frozen freeze-dry sample preparations were employed. Ion redistribution artifacts in conventional chemical preparations are discussed. Cryogenically prepared freeze-fractured freeze-dried cultured cells allowed the three-dimensional ion microscopic imaging of elements. As smaller structures in calcium images can be resolved with the 0.5 [mu]m spatial resolution, correlative techniques are needed to confirm their identity. The potentials of reflected light microscopy, scanning electron microscopy and laser scanning confocal microscopy are discussed for microfeature recognition in freeze-fractured freeze-dried cells. The feasibility of using frozen freeze-dried cells for imaging molecular transport at subcellular resolution was tested. Ion microscopy successfully imaged the transport of the isotopically tagged (13C, 15N) amino acid, -arginine. The labeled amino acid was imaged at mass 28 with a Cs+ primary ion beam as the 28(13C15N)- species. After a 4 h exposure of LLC-PK1 kidney cells to 4 mM labeled arginine, the amino acid was localized throughout the cell with a preferential incorporation into the nucleus and nucleolus. An example is also shown of the ion microscopic imaging of sodium borocaptate, an experimental therapeutic drug for brain tumors, in cryogenically prepared frozen freeze-dried Swiss 3T3 cells.

  10. A new vibrational level of the H2+ molecular ion

    NASA Astrophysics Data System (ADS)

    Carbonell, J.; Lazauskas, R.; Delande, D.; Hilico, L.; Kiliç, S.

    2003-11-01

    A new vibrational level of the H2+ molecular ion with binding energy of 1.09 × 10-9 a.u. approx 30 neV below the first dissociation limit is predicted, using highly accurate numerical non-relativistic quantum calculations, which go beyond the Born-Oppenheimer approximation. It is the first-excited vibrational level v = 1 of the 2pσu electronic state, antisymmetric with respect to the exchange of the two protons, with orbital angular momentum L = 0. It manifests itself as a huge p-H scattering length of a = 750 ± 5 Bohr radii.

  11. Multiple ionization bursts in laser-driven hydrogen molecular ion.

    PubMed

    Takemoto, Norio; Becker, Andreas

    2010-11-12

    Theoretical study on H2(+) in an intense infrared laser field on the attosecond time scale reveals that the molecular ion shows multiple bursts of ionization within a half-cycle of the laser field oscillation, in contrast to the widely accepted tunnel ionization picture for an atom. These bursts are found to be induced by transient localization of the electron at one of the nuclei, and a relation between the time instants of the localization and the vector potential of the laser light is derived. A scheme is proposed to probe the localization dynamics by an extreme ultraviolet laser pulse. PMID:21231228

  12. High-precision spectroscopy of hydrogen molecular ions

    NASA Astrophysics Data System (ADS)

    Zhong, Zhen-Xiang; Tong, Xin; Yan, Zong-Chao; Shi, Ting-Yun

    2015-05-01

    In this paper, we overview recent advances in high-precision structure calculations of the hydrogen molecular ions ( and HD+), including nonrelativistic energy eigenvalues and relativistic and quantum electrodynamic corrections. In combination with high-precision measurements, it is feasible to precisely determine a molecular-based value of the proton-to-electron mass ratio. An experimental scheme is presented for measuring the rovibrational transition frequency (v,L) : (0,0) → (6,1) in HD+, which is currently underway at the Wuhan Institute of Physics and Mathematics. Project supported by the National Natural Science Foundation of China (Grants Nos. 11474316, 11004221, 10974224, and 11274348), the “Hundred Talent Program” of Chinese Academy of Sciences. Yan Zong-Chao was supported by NSERC, SHARCnet, ACEnet of Canada, and the CAS/SAFEA International Partnership Program for Creative Research Teams.

  13. Energetic atomic and molecular ions in Saturn's magnetosphere

    SciTech Connect

    Hamilton, D.C.; Brown, D.C.; Gloeckler, G.; Axford, W.I.

    1983-11-01

    We present observations and anlysis of the composition, energy spectra and spatial distribution of energetic ions (> or approx. =0.2 MeV/nucleon) in Saturn's magnetosphere outside of approx.4 R/sub S/. Our results are based on data from the low-energy particle telescope (LEPT), one of the two sensors of the low-energy charged particle (LECP) experiment on Voyager 1 and 2. The major species, in order of abundance, are H, H/sub 2//sup +/, He, H/sub 3//sup +/, C, and O. The energy spectra of the magnetospheric ions are typically very soft (..gamma..approx.6-7), with an apparent cutoff in energy/charge at 1--2 MeV/e. From the abundance ratios we conclude that the energetic He, C, and O ions have a solar wind origin. The molecular hydrogen ions H/sub 2//sup +/, and H/sub 3//sup +/ probably originate from Saturn's upper ionosphere. The protons can originate from the solar wind, the ionosphere or the hydrogen atom torus in Saturn's outer magnetosphere. The local H/sup +/ sources apparently were dominant at the time of Voyager 1 encouter, but the solar wind may also have been an important source at the time of Voyager 2. To explain the fact that the energetic heavy ions (Z> or =6, E> or approx. =0.2 MeV/nucleon) are apparently of solar wind origin, an acceleration process that favors ions with small mass/charge ionized solar wind particles even though singly or doubly charged local ions (e.g. O/sup +/, O/sup + +/, N/sup +/, etc.) have been observed to be much more abundant in the low-energy magnetospheric plasma. Energization may involve a two-step process of electrostatic iacceleration in the tail region combined with inward radial diffusion. The fluxes of all species decreased inside the orbit of Dione and were nearlly wiped out in the ''slot'' region within the orbit of Tethys.

  14. Photodissociation spectroscopy of the dysprosium monochloride molecular ion

    NASA Astrophysics Data System (ADS)

    Dunning, Alexander; Petrov, Alexander; Schowalter, Steven J.; Puri, Prateek; Kotochigova, Svetlana; Hudson, Eric R.

    2015-09-01

    We have performed a combined experimental and theoretical study of the photodissociation cross section of the molecular ion DyCl+. The photodissociation cross section for the photon energy range 35 500 cm-1 to 47 500 cm-1 is measured using an integrated ion trap and time-of-flight mass spectrometer; we observe a broad, asymmetric profile that is peaked near 43 000 cm-1. The theoretical cross section is determined from electronic potentials and transition dipole moments calculated using the relativistic configuration-interaction valence-bond and coupled-cluster methods. The electronic structure of DyCl+ is extremely complex due to the presence of multiple open electronic shells, including the 4f10 configuration. The molecule has nine attractive potentials with ionically bonded electrons and 99 repulsive potentials dissociating to a ground state Dy+ ion and Cl atom. We explain the lack of symmetry in the cross section as due to multiple contributions from one-electron-dominated transitions between the vibrational ground state and several resolved repulsive excited states.

  15. Photoionization and photofragmentation of the C60+ molecular ion

    NASA Astrophysics Data System (ADS)

    Baral, K. K.; Aryal, N. B.; Esteves-Macaluso, D. A.; Thomas, C. M.; Hellhund, J.; Lomsadze, R.; Kilcoyne, A. L. D.; Müller, A.; Schippers, S.; Phaneuf, R. A.

    2016-03-01

    Cross-section measurements are reported for single and double photoionization of C60+ ions in the photon energy range 18-150 eV accompanied by the loss of zero to seven pairs of carbon atoms, as well as for fragmentation without ionization resulting in loss of two to eight pairs of C atoms in the photon energy range 18-65 eV. Absolute measurements were performed by merging a beam of C60+ molecular ions with a beam of monochromatized synchrotron radiation. Product channels involving dissociation yielding smaller fullerene fragment ions account for nearly half of the total measured oscillator strength in this energy range. The sum of cross sections for the measured product channels is compared to a published calculation of the total photoabsorption cross section of neutral C60 based on time-dependent density-functional theory. This comparison and an accounting of oscillator strengths indicate that with the exception of C58+, the most important product channels resulting from photoabsorption were accounted for in the experiment. Threshold energies for the successive removal of carbon atom pairs accompanying photoionization are also determined from the measurements.

  16. Photodissociation spectroscopy of the dysprosium monochloride molecular ion.

    PubMed

    Dunning, Alexander; Petrov, Alexander; Schowalter, Steven J; Puri, Prateek; Kotochigova, Svetlana; Hudson, Eric R

    2015-09-28

    We have performed a combined experimental and theoretical study of the photodissociation cross section of the molecular ion DyCl(+). The photodissociation cross section for the photon energy range 35,500 cm(-1) to 47,500 cm(-1) is measured using an integrated ion trap and time-of-flight mass spectrometer; we observe a broad, asymmetric profile that is peaked near 43,000 cm(-1). The theoretical cross section is determined from electronic potentials and transition dipole moments calculated using the relativistic configuration-interaction valence-bond and coupled-cluster methods. The electronic structure of DyCl(+) is extremely complex due to the presence of multiple open electronic shells, including the 4f(10) configuration. The molecule has nine attractive potentials with ionically bonded electrons and 99 repulsive potentials dissociating to a ground state Dy(+) ion and Cl atom. We explain the lack of symmetry in the cross section as due to multiple contributions from one-electron-dominated transitions between the vibrational ground state and several resolved repulsive excited states. PMID:26429013

  17. Photodissociation spectroscopy of the dysprosium monochloride molecular ion

    SciTech Connect

    Dunning, Alexander Schowalter, Steven J.; Puri, Prateek; Hudson, Eric R.; Petrov, Alexander; Kotochigova, Svetlana

    2015-09-28

    We have performed a combined experimental and theoretical study of the photodissociation cross section of the molecular ion DyCl{sup +}. The photodissociation cross section for the photon energy range 35 500 cm{sup −1} to 47 500 cm{sup −1} is measured using an integrated ion trap and time-of-flight mass spectrometer; we observe a broad, asymmetric profile that is peaked near 43 000 cm{sup −1}. The theoretical cross section is determined from electronic potentials and transition dipole moments calculated using the relativistic configuration-interaction valence-bond and coupled-cluster methods. The electronic structure of DyCl{sup +} is extremely complex due to the presence of multiple open electronic shells, including the 4f{sup 10} configuration. The molecule has nine attractive potentials with ionically bonded electrons and 99 repulsive potentials dissociating to a ground state Dy{sup +} ion and Cl atom. We explain the lack of symmetry in the cross section as due to multiple contributions from one-electron-dominated transitions between the vibrational ground state and several resolved repulsive excited states.

  18. Development of a sensitive mid-infrared spectrometer for the study of cooled molecular ions

    NASA Astrophysics Data System (ADS)

    Porambo, Michael W.

    The study of molecular ions is relevant to many areas of scientific interest. Mid-infrared laser spectroscopy functions as a useful tool for understanding the role of molecular ions in these areas. To this end, a broadly tunable mid-infrared difference frequency generation noise-immune cavity-enhanced optical heterodyne molecular spectroscopy (NICE-OHMS) system has been developed and characterized through rovibrational spectroscopy of methane. In addition, an attempt was made to use this spectrometer to probe molecular ions focused into an ion beam. Challenges inherent to laboratory molecular ion spectroscopy, such as quantum dilution at high internal temperatures and low ion number density, have been addressed through the development of an instrument that produces rotationally cooled molecular ions coupled to the highly sensitive spectroscopic technique NICE-OHMS. The instrument was first explored as an extension of an ion beam spectrometer by the integration of a continuous supersonic expansion discharge source for the production of the cooled molecular ions. Issues with the implementation led to the re- design of the instrument for spectroscopically probing a supersonic expansion discharge directly with NICE-OHMS. After implementing discharge modulation of the supersonic expansion source, spectra of rotationally cooled H(3/+) and HN(+/2) were acquired. This instrumental development and preliminary spectroscopy has paved the way for a new method for the sensitive spectroscopic study of cooled molecular ions that will aid further insight into these chemical species in many fields.

  19. Molecular Dynamical Study on Ion Channeling through Peptide Nanotube

    NASA Astrophysics Data System (ADS)

    Sumiya, Norihito; Igami, Daiki; Takeda, Kyozaburo

    2011-12-01

    We theoretically study the possibility of ion channeling through peptide nanotubes (PNTs). After designing the minimal peptide nanorings (PNRs) and their aggregated form (peptide nanotubes, PNT) computationally, we carry out molecular dynamics (MD) calculations for cation channeling. The present MD calculations show that cation channeling through PNTs occurs. Furthermore, inter-ring hydrogen bonds (HBs) survive and maintain the tubular form of PNTs during cation channeling. We introduce mobility such that cation channeling can be evaluated quantitatively. As the ionic radius of the cation becomes smaller, the effective relaxation time τ becomes larger. Accordingly, mobilities of 10-2˜10-3[cm2/volt/sec] are calculated. In contrast, when an anion (F-) passes through the PNT, the inter-ring HBs are broken, thus inducing breakdown of the peptide backbone. Consequently, H atoms from the broken HBs surround the channeling anion (F-) and halt its motion.

  20. Ion and Molecular Recognition Using Aryl–Ethynyl Scaffolding

    PubMed Central

    Vonnegut, Chris L.; Tresca, Blakely W.

    2015-01-01

    The aryl–ethynyl linkage has been extensively employed in the construction of hosts for a variety of guests. Uses range from ion detection (e.g., of metal cations in the environment or industrial waste and of anions prevalent in nature), to molecular mimics for biological systems, and to applications targeting future safety issues (such as CO2 capture and indicators for the manufacture of chemical weapons). This Focus Review examines the utilization of the aryl–ethynyl linkage in engineering host molecules for a variety of different guests, and how the alkyne unit plays an integral part as both a rigid scaffolding section in host geometry design as well as a linker to allow conjugative communication between discrete π-electron systems. PMID:25586943

  1. Ion and molecular recognition using aryl-ethynyl scaffolding.

    PubMed

    Vonnegut, Chris L; Tresca, Blakely W; Johnson, Darren W; Haley, Michael M

    2015-03-01

    The aryl-ethynyl linkage has been extensively employed in the construction of hosts for a variety of guests. Uses range from ion detection (e.g., of metal cations in the environment or industrial waste and of anions prevalent in nature), to molecular mimics for biological systems, and to applications targeting future safety issues (such as CO2 capture and indicators for the manufacture of chemical weapons). This Focus Review examines the utilization of the aryl-ethynyl linkage in engineering host molecules for a variety of different guests, and how the alkyne unit plays an integral part as both a rigid scaffolding section in host geometry design as well as a linker to allow conjugative communication between discrete π-electron systems. PMID:25586943

  2. Molecular ions in the protostellar shock L1157-B1

    NASA Astrophysics Data System (ADS)

    Podio, L.; Lefloch, B.; Ceccarelli, C.; Codella, C.; Bachiller, R.

    2014-05-01

    Aims: We perform a complete census of molecular ions with an abundance greater than ~10-10 in the protostellar shock L1157-B1. This allows us to study the ionisation structure and chemistry of the shock. Methods: An unbiased high-sensitivity survey of L1157-B1 performed with the IRAM-30 m and Herschel/HIFI as part of the CHESS and ASAI large programmes allows searching for molecular ions emission. Then, by means of a radiative transfer code in the large velocity gradient approximation, the gas physical conditions and fractional abundances of molecular ions are derived. The latter are compared with estimates of steady-state abundances in the cloud and their evolution in the shock calculated with the chemical model Astrochem. Results: We detect emission from HCO+, H13CO+, N2H+, HCS+, and for the first time in a shock, from HOCO+ and SO+. The bulk of the emission peaks at blue-shifted velocity, ~0.5-3 km s -1 with respect to systemic, has a width of ~3-7 km s-1 and is associated with the outflow cavities (Tkin ~ 20-70 K, nH2 ~ 105 cm-3). A high-velocity component up to -40 km s-1, associated with the primary jet, is detected in the HCO+ 1-0 line. Observed HCO+ and N2H+ abundances (XHCO+ ~ 0.7-3 × 10-8, XN2H+ ~ 0.4-8 × 10-9) agree with steady-state abundances in the cloud and with their evolution in the compressed and heated gas in the shock for cosmic rays ionisation rate ζ = 3 × 10-16 s-1. HOCO+, SO+, and HCS+ observed abundances (XHOCO+ ~ 10-9, XSO+ ~ 8 × 10-10, XHCS+ ~ 3-7 × 10-10), instead, are 1-2 orders of magnitude larger than predicted in the cloud; on the other hand, they are strongly enhanced on timescales shorter than the shock age (~2000 years) if CO2, S or H2S, and OCS are sputtered off the dust grains in the shock. Conclusions: The performed analysis indicates that HCO+ and N2H+ are a fossil record of pre-shock gas in the outflow cavity, whilst HOCO+, SO+, and HCS+ are effective shock tracers that can be used to infer the amount of CO2 and sulphur

  3. Cluster ion beam profiling of organics by secondary ion mass spectrometry--does sodium affect the molecular ion intensity at interfaces?

    PubMed

    Green, Felicia M; Gilmore, Ian S; Seah, Martin P

    2008-12-01

    The use of cluster ion beam sputtering for depth profiling organic materials is of growing technological importance and is a very active area of research. At the 44th IUVSTA Workshop on "Sputtering and Ion Emission by Cluster Ion Beams", recent results were presented of a cluster ion beam depth profile of a thin organic molecular layer on a silicon wafer substrate. Those data showed that the intensity of molecular secondary ions is observed to increase at the interface and this was explained in terms of the higher stopping power in the substrate and a consequently higher sputtering yield and even higher secondary ion molecular sputtering yield. An alternative hypothesis was postulated in the workshop discussion which may be paraphrased as: "under primary ion bombardment of an organic layer, mobile ions such as sodium may migrate to the interface with the inorganic substrate and this enhancement of the sodium concentration increases the ionisation probability, so increasing the molecular ion yield observed at the interface". It is important to understand if measurement artefacts occur at interfaces for quantification as these are of great technological relevance - for example, the concentration of drug in a drug delivery system. Here, we evaluate the above hypothesis using a sample that exhibits regions of high and low sodium concentration at both the organic surface and the interface with the silicon wafer substrate. There is no evidence to support the hypothesis that the probability of molecular secondary ion ionisation is related to the sodium concentration at these levels. PMID:19039819

  4. Molecular designs for controlling the local environments around metal ions.

    PubMed

    Cook, Sarah A; Borovik, A S

    2015-08-18

    The functions of metal complexes are directly linked to the local environment in which they are housed; modifications to the local environment (or secondary coordination sphere) are known to produce changes in key properties of the metal centers that can affect reactivity. Noncovalent interactions are the most common and influential forces that regulate the properties of secondary coordination spheres, which leads to complexities in structure that are often difficult to achieve in synthetic systems. Using key architectural features from the active sites of metalloproteins as inspiration, we have developed molecular systems that enforce intramolecular hydrogen bonds (H-bonds) around a metal center via incorporation of H-bond donors and acceptors into rigid ligand scaffolds. We have utilized these molecular species to probe mechanistic aspects of biological dioxygen activation and water oxidation. This Account describes the stabilization and characterization of unusual M-oxo and heterobimetallic complexes. These types of species have been implicated in a range of oxidative processes in biology but are often difficult to study because of their inherent reactivity. Our H-bonding ligand systems allowed us to prepare an Fe(III)-oxo species directly from the activation of O2 that was subsequently oxidized to form a monomeric Fe(IV)-oxo species with an S = 2 spin state, similar to those species proposed as key intermediates in non-heme monooxygenases. We also demonstrated that a single Mn(III)-oxo center that was prepared from water could be converted to a high-spin Mn(V)-oxo species via stepwise oxidation, a process that mimics the oxidative charging of the oxygen-evolving complex (OEC) of photosystem II. Current mechanisms for photosynthetic O-O bond formation invoke a Mn(IV)-oxyl species rather than the isoelectronic Mn(V)-oxo system as the key oxidant based on computational studies. However, there is no experimental information to support the existence of a Mn

  5. Polarizabilities and Other Properties of the td Muons Molecular Ion

    NASA Technical Reports Server (NTRS)

    Bhatia, A. K.; Drachman, Richard J.; Fisher, Richard R. (Technical Monitor)

    2001-01-01

    Wavefunctions of Hylleraas type were used earlier to calculate energy levels of muonic systems. Recently, we found in the case of the molecular ions H2+, D2+ and HD+ that it was necessary to include high powers of the internuclear distance in the Hylleraas functions to localize the nuclear motion when treating the ions as three-body systems without invoking the Born-Oppenheimer approximation. We try the same approach in a muonic system, td(mu-). Improved convergence is obtained for J = 0 and 1 states for shorter expansions when we use this type of generalized Hylleraas function, but as the expansion length increases the high powers are no longer useful. We obtain good energy values for the two lowest J = 0 and J = 1 states and compare them with the best earlier calculations. Expectation values are obtained for various operators, the Fermi contact parameters, and the permanent quadrupole moment. The cusp conditions are also calculated. The polarizability of the ground state is then calculated using second-order perturbation theory with intermediate J = 1 pseudostates. It should be possible to measure the polarizability by observing Rydberg states of atoms with td(mu-) acting as the nucleus.

  6. Molecular lanthanide single-ion magnets: from bulk to submonolayers.

    PubMed

    Dreiser, J

    2015-05-13

    Single-ion magnets (SIMs) are mononuclear molecular complexes exhibiting slow relaxation of magnetization. They are currently attracting a lot of interest because of potential applications in spintronics and quantum information processing. However, exploiting SIMs in, e.g. molecule-inorganic hybrid devices requires a fundamental understanding of the effects of molecule-substrate interactions on the SIM magnetic properties. In this review the properties of lanthanide SIMs in the bulk crystalline phase and deposited on surfaces in the (sub)monolayer regime are discussed. As a starting point trivalent lanthanide ions in a ligand field will be described, and the challenges in characterizing the ligand field are illustrated with a focus on several spectroscopic techniques which are able to give direct information on the ligand-field split energy levels. Moreover, the dominant mechanisms of magnetization relaxation in the bulk phase are discussed followed by an overview of SIMs relevant for surface deposition. Further, a short introduction will be given on x-ray absorption spectroscopy, x-ray magnetic circular dichroism and scanning tunneling microscopy. Finally, the recent experiments on surface-deposited SIMs will be reviewed, along with a discussion of future perspectives. PMID:25893740

  7. Molecular dynamics simulation of graphene bombardment with Si ion

    NASA Astrophysics Data System (ADS)

    Qin, Xin-Mao; Gao, Ting-Hong; Yan, Wan-Jun; Guo, Xiao-Tian; Xie, Quan

    2014-03-01

    Molecular dynamics simulations with Tersoff-Ziegler-Biersack-Littmark (Tersoff-ZBL) potential and adaptive intermolecular reactive empirical bond order (AIREBO) potential are performed to study the effect of irradiated graphene with silicon ion at several positions and energy levels of 0.1-1000 eV. The simulations reveal four processes: absorption, replacement, transmission and damage. At energies below 110 eV, the dominant process is absorption. For atom in group (a), the process that takes place is replacement, in which the silicon ion removes one carbon atom and occupies the place of the eliminated atom at the incident energy of 72-370 eV. Transmission is present at energies above 100 eV for atom in group (d). Damage is a very important process in current bombardment, and there are four types of defects: single vacancy, replacement-single vacancy, double vacancy and nanopore. The simulations provide a fundamental understanding of the silicon bombardment of graphene, and the parameters required to develop graphene-based devices by controlling defect formation.

  8. Ab initio molecular dynamics calculations of ion hydration free energies

    SciTech Connect

    Leung, Kevin; Rempe, Susan B.; Lilienfeld, O. Anatole von

    2009-05-28

    We apply ab initio molecular dynamics (AIMD) methods in conjunction with the thermodynamic integration or '{lambda}-path' technique to compute the intrinsic hydration free energies of Li{sup +}, Cl{sup -}, and Ag{sup +} ions. Using the Perdew-Burke-Ernzerhof functional, adapting methods developed for classical force field applications, and with consistent assumptions about surface potential ({phi}) contributions, we obtain absolute AIMD hydration free energies ({Delta}G{sub hyd}) within a few kcal/mol, or better than 4%, of Tissandier et al.'s [J. Phys. Chem. A 102, 7787 (1998)] experimental values augmented with the SPC/E water model {phi} predictions. The sums of Li{sup +}/Cl{sup -} and Ag{sup +}/Cl{sup -} AIMD {Delta}G{sub hyd}, which are not affected by surface potentials, are within 2.6% and 1.2 % of experimental values, respectively. We also report the free energy changes associated with the transition metal ion redox reaction Ag{sup +}+Ni{sup +}{yields}Ag+Ni{sup 2+} in water. The predictions for this reaction suggest that existing estimates of {Delta}G{sub hyd} for unstable radiolysis intermediates such as Ni{sup +} may need to be extensively revised.

  9. Novel Metal Ion Based Estrogen Mimics for Molecular Imaging

    SciTech Connect

    Rajagopalan, Raghavan

    2006-01-30

    The overall objective of the SBIR Phase I proposal is to prepare and evaluate a new class of {sup 99m}Tc or {sup 94m}Tc containing estrogen-like small molecules ('estrogen mimics') for SPECT or PET molecular imaging of estrogen receptor positive (ER+) tumors. In this approach, the metal ion is integrated into the estrone skeleton by isosteric substitution of a carbon atom in the steroidal structure to give new class of mimics that are topologically similar to the native estrogen (Fig. 1). Although both N{sub 2}S{sub 2} and N{sub 3}S mimics 1 and 2 were considered as target structures, molecular modeling study revealed that the presence of the acetyl group at position-15 in the N{sub 3}S mimic 2 causes steric hinderance toward binding of 2 to SHBG. Therefore, initial efforts were directed at the synthesis and evaluation of the N{sub 2}S{sub 2} mimic 1.

  10. Spectroscopic identification of isomeric jet-cooled benzyl-type radicals formed from 3-fluoro-o-xylene by corona discharge

    NASA Astrophysics Data System (ADS)

    Yoon, Young Wook; Chae, Sang Youl; Lee, Sang Kuk

    2013-10-01

    By means of a pinhole-type glass nozzle designed for supersonic jet expansion along with corona discharge, vibronically excited but jet-cooled isomeric benzyl-type radicals were generated from the precursor 3-fluoro-o-xylene. The visible vibronic emission spectrum was recorded from the discharge system with a long-path monochromator. From an analysis of the spectrum observed, we identified the formation of two isomers, 2-methyl-3-fluorobenzyl and 2-methyl-6-fluorobenzyl radicals in the corona discharge of precursor, and determined for the first time the electronic energy in the D1 → D0 transition and vibrational mode frequencies in the D0 state for both isomers.

  11. Jet-cooled laser-induced fluorescence spectroscopy of ScH: Observation of an Ω‧=2-Ω″=1 transition

    NASA Astrophysics Data System (ADS)

    Mukund, Sheo; Bhattacharyya, Soumen; Nakhate, S. G.

    2014-11-01

    New bands of scandium monohydride at origins 17,914.5 and 17,942.3 cm-1 have been observed in a jet-cooled beam with laser-induced fluorescence spectroscopy. Mass-selected resonant photoionization spectroscopy also confirmed the carrier of the band as ScH. The rotational analysis indicated that both transitions at 17,914.5 and 17,942.3 cm-1 are of Ω‧=2-Ω″=1 type with vibrational assignments (0,0) and (1,1) respectively. The assigned g3Φ2-a3Δ1 excitation is the first observed triplet-triplet transition in ScH.

  12. Improved electron ionization ion source for the detection of supersonic molecular beams

    NASA Astrophysics Data System (ADS)

    Amirav, Aviv; Fialkov, Alexander; Gordin, Alexander

    2002-08-01

    An improved electron ionization (EI) ion source is described, based on the modification of a Brink-type EI ion source through the addition of a second cage with a fine mesh outside the ion chamber. The added outer cage shields the inner ion cage (ionization zone) against the penetration of the filament and electron repeller potentials, and thus results in the provision of ions with narrower ion energy distribution, hence improved ion-beam quality. The closer to zero electrical field inside the ion cage enables improved filtration (rejection) of ions that are produced from vacuum background compounds, based on difference in ion energies of beam and background species. The improved background ion filtration and ion-beam quality resulted in 2.6 times higher mass spectrometric ion signal, combined with 6.4 times better signal to noise ratio, in comparison with the same ion source having a single cage. The dual cage ion source further provides a smaller or no reduction of the electron emission current upon lowering the electron energy for achieving softer EI and/or electron attachment ionization. It also improves the long-term mass spectral and signal reproducibility and enables fast, automated change of the electron energy. Consequently, the dual cage EI ion source is especially effective for use with gas chromatography mass spectrometry with supersonic molecular beams (SMB), liquid chromatography mass spectrometry with SMB, ion guns with SMB, and any other experimental systems with SMB or nonthermal molecular beams.

  13. Plant sunscreens in the UV-B: ultraviolet spectroscopy of jet-cooled sinapoyl malate, sinapic acid, and sinapate ester derivatives.

    PubMed

    Dean, Jacob C; Kusaka, Ryoji; Walsh, Patrick S; Allais, Florent; Zwier, Timothy S

    2014-10-22

    Ultraviolet spectroscopy of sinapoyl malate, an essential UV-B screening agent in plants, was carried out in the cold, isolated environment of a supersonic expansion to explore its intrinsic UV spectral properties in detail. Despite these conditions, sinapoyl malate displays anomalous spectral broadening extending well over 1000 cm(-1) in the UV-B region, presenting the tantalizing prospect that nature's selection of UV-B sunscreen is based in part on the inherent quantum mechanical features of its excited states. Jet-cooling provides an ideal setting in which to explore this topic, where complications from intermolecular interactions are eliminated. In order to better understand the structural causes of this behavior, the UV spectroscopy of a series of sinapate esters was undertaken and compared with ab initio calculations, starting with the simplest sinapate chromophore sinapic acid, and building up the ester side chain to sinapoyl malate. This "deconstruction" approach provided insight into the active mechanism intrinsic to sinapoyl malate, which is tentatively attributed to mixing of the bright V ((1)ππ*) state with an adiabatically lower (1)nπ* state which, according to calculations, shows unique charge-transfer characteristics brought on by the electron-rich malate side chain. All members of the series absorb strongly in the UV-B region, but significant differences emerge in the appearance of the spectrum among the series, with derivatives most closely associated with sinapoyl malate showing characteristic broadening even under jet-cooled conditions. The long vibronic progressions, conformational distribution, and large oscillator strength of the V (ππ*) transition in sinapates makes them ideal candidates for their role as UV-B screening agents in plants. PMID:25295994

  14. Nonlinear effects in desorption of valine with fast incident molecular ions

    SciTech Connect

    Salehpour, M.; Fishel, D.L.; Hunt, J.E.

    1988-12-15

    Fast molecular ions as primary particles have been used to study secondary-ion desorption from organic layers. The secondary molecular-ion yield of the amino acid valine (molecular weight, 117) has been measured as a function of the velocity of primary atomic and molecular incident ions. The primary ions used were C/sup +/, O/sup +/, Ar/sup +/, C/sub 2//sup +/, O/sub 2//sup +/ , CO/sup +/, CO/sub 2//sup +/, CH/sup +/, CH/sub 3//sup +/, CF/sup +/, CF/sub 3//sup +/, C/sub 3/F/sub 5//sup +/, and C/sub 4/F/sub 7//sup +/ in the energy range 600 keV--3.7 MeV. The secondary molecular-ion yields, when compared to yields for atomic constituents, unambiguously show that collective effects exist in desorption with incident molecular ions. Results are discussed in the framework of enhancement in the electronic stopping power per atom for molecular ions due to the vicinage of the fast-moving charges in the material. The resulting high-yield enhancements, especially with the use of large incident ions such as C/sub 3/F/sub 5//sup +/ and C/sub 4/F/sub 7//sup +/, are very encouraging for the future of mass spectrometry of large organic molecules.

  15. Laser mass spectrometry of biological molecular ions produced by matrix assisted laser desorption ionization (MALDI)

    NASA Astrophysics Data System (ADS)

    Jia, W. J.; Kosmidis, C.; Ledingham, K. W. D.; Scott, C. T. J.; Singhal, R. P.

    1996-10-01

    A tandem reflectron laser mass spectrometer is used for investigations of the photo fragmentation of molecular ions. The observed fragmentation patterns for 2,5-dihydrobenzoic acid and its fragments ions are analysed. PTH-trytophan and PTH-valine ions, generated by MALDI, are photodissociated and their fragmentation pattern is discussed.

  16. Mechanism of fragmentation and atomization of molecular ions in gasdynamic transport cell

    NASA Astrophysics Data System (ADS)

    Bazhenov, A. N.; Bulovich, S. V.; Gall, L. N.; Kretinina, A. V.; Lapushkin, M. N.; Gall, N. R.

    2010-04-01

    The fragmentation of molecular ions formed upon the electrospraying of a sample and transported through the gasdynamic system of a mass spectrometer equipped with an IESAP (Ion Extraction from Solution at Atmospheric Pressure) source has been experimentally studied. It is established that ion fragmentation in a Kantorowicz-Gray type cell takes place in the immediate vicinity of a skimmer port, apparently, as a result of collisions between ions (accelerated in an electric field) and stagnant gas. Molecular mechanisms of fragmentation are considered and it is concluded that this process can take place in a single ion-molecule collision event.

  17. On the sources of energization of molecular ions at ionospheric altitudes

    SciTech Connect

    Peterson, W.K.; Abe, T.; Fukunishi, H.; Greffen, M.J.; Hayakawa, H.; Kasahara, Y.; Kimura, I.; Matsuoka, A.; Mukai, T.; Nagatsuma, T. ||||

    1994-12-01

    During geomagnetically active times, the suprathermal mass spectrometer on the Akebono satellite frequency observes upflowing molecular ions (NO(+), N2(+), O2(+)) in the 2-3 Earth radii geocentric distance regions in the auroral zone. Molecular ions originating at ionospheric altitudes must acquire an energy of the order of 10 eV in order to overcome gravitation and reach altitudes greater than 2 R(sub E). This energy must be acquired in a time short compared with the local dissociative recombination lifetime of the ions; the latter is of the order of minutes in the F region ionosphere (300-500 km altitude). Upflowing molecular ions thus provide a test particle probe into the mechanisms responsible for heavy ion escape from the ionosphere. In this paper we analyze the extensive complement of plasma, field, and wave data obtained on the Akebono satellite in a number of upflowing molecular ion events observed at high altitudes (5000-10,000 km). We use these data to investigate the source of energization of the molecular ions at ionospheric altitudes. We show that Joule heating and ion resonance heating do not transfer enough energy or do not transfer it fast enough to account for the observed fluxes of upflowing molecular ions. We found that the observed field-aligned currents were too weak to support large-scale field-aligned current instabilities at ionospheric altitudes.

  18. Counter-ion distribution around flexible polyelectrolytes having different molecular architecture.

    PubMed

    Chremos, Alexandros; Douglas, Jack F

    2016-03-21

    We explore the monovalent counter-ion distribution around flexible highly-charged polyelectrolytes with different molecular architectures (linear chains, stars, and unknotted and trefoil rings) using molecular dynamics simulations that include an explicit solvent that interacts with the polyelectrolyte. In particular, we find that the molecular topology influences the fraction of counter-ions transiently associating with the polyelectrolyte on a scale of the order of the chain segments, forming a "condensed" counter-ion interfacial layer. As with the hydrogen bonding of water to proteins and other polymers, the persistence time of these interfacial "bound" counter-ions is relatively short, O(1 ps), and we characterize the fluctuations in the number of the counter-ions populating the interfacial layer. We also find that the counter-ions are distributed in a non-uniform fashion on the polyelectrolyte backbone, forming dynamical clusters whose form and average size is sensitive to molecular architecture. In addition, we find that the residual bound counter-ions, not located in either the interfacial layer or the bulk solution, form a diffuse ionic cloud around the polyelectrolyte due to the uncompensated polyelectrolyte charge along the backbone. Generally charge valence strongly influences the extent of the diffuse counter-ion cloud, but in the case of monovalent counter-ions, we find that the size of the diffuse counter-ion cloud nearly coincides with the polyelectrolyte radius of gyration, independent of molecular topology. PMID:26864861

  19. Photovoltaic lithium-ion battery fabricated by molecular precursor method

    NASA Astrophysics Data System (ADS)

    Nagai, Hiroki; Suzuki, Tatsuya; Takahashi, Yoshihisa; Sato, Mitsunobu

    2016-06-01

    A novel thin-film lithium-ion battery (LIB) which can be charged by the light irradiation was fabricated by molecular precursor method. The unprecedented, translucent thin-film LIB, fabricated on a fluorine-doped tin oxide pre-coated glass substrate, was attained by using the active materials, titania for anode and LiCoO2 for cathode, respectively. The averaged potential at 2.04V was observed by applying a constant current of 0.2mA. Then, that at 1.82V was detected after 60s during the sequential self-discharge process. The charging voltage of the assembled battery was 1.38V with irradiation of 1-sun, the self-discharge voltage was 1.37V. Based on the calibration curve of the charging voltages over constant currents ranging from 0-1.0mA, the detected value can be theoretically reduced to the charging operation by applying a constant current of approximately 60μA. The charge and discharge of this device was stable voltage at least 30 cycles. The two-in-one device can simultaneously generate and store electricity from solar light, the renewable energy source, and may be applied in smart windows for distributed power system according to on-site demand.

  20. Molecular ions in the laboratory and in space

    SciTech Connect

    McCarthy, Michael C.

    2015-01-22

    Molecular ions play a central role in the gas-phase chemistry of the interstellar medium; they also provide information on the physical conditions in astronomical sources (e.g., fractional ionization), and in some cases can be used to infer the abundance of nonpolar molecules such as N{sub 2} and CO{sub 2} which can not be observed in the radio band. During the past four years, the rotational spectra of six carbon-chain anions (C{sub 2}H{sup −}, C{sub 4}H{sup −}, C{sub 6}H{sup −}, C{sub 8}H{sup −}, CN{sup −}, C{sub 3}N{sup −}), NCO{sup −} and seven protonated species (HSCO{sup +}, HSCS{sup +}, cis- and trans-HOSO{sup +}, H{sub 2}NCO{sup +}, HNCOH{sup +}, and HNNO{sup +}) have been detected in our laboratory. On the basis of dedicated astronomical searches, all of the carbon-chain anions except C{sub 2}H{sup −} have now been identified in space. In addition to highlighting recent work on carbon-chain anions and protonated HSO{sub 2}{sup +}, efforts to better understand the distribution of anions in space using C{sub 6}H{sup −} as a tracer for negative charge are described.

  1. Molecular dynamics simulation of ion focusing and crowdion formation in self-ion-irradiated Fe

    NASA Astrophysics Data System (ADS)

    Chen, Di; Shao, Lin

    2012-02-01

    We have used molecular dynamics (MD) simulation to investigate damage and defect development in a <1 0 0> Fe substrate upon 2 keV Fe ion bombardment. The damage cascade formation is accompanied by atomic shifting over a limited distance along the direction of one atomic row, which leads to formation of crowdions aligned with <1 1 1> direction. At the end of structural relaxation and defect recombination, crowdions lead to formation of dumbbell defects - a type of vacancy-interstitial complexes having one vacancy between a pair of slightly displaced interstitials. The dumbbell defects are initially oriented along <1 1 1> direction. After a typical period of 0.2 ps, some dumbbell defects rotate towards <1 1 0> direction. Crowdion and dumbbell defect formation influence the time dependent damage buildups.

  2. Superstatistical velocity distributions of cold trapped ions in molecular-dynamics simulations

    NASA Astrophysics Data System (ADS)

    Rouse, I.; Willitsch, S.

    2015-11-01

    We present a realistic molecular-dynamics treatment of laser-cooled ions in radio-frequency ion traps which avoids previously made simplifications such as modeling laser cooling as a friction force and combining individual heating mechanisms into a single effective heating force. Based on this implementation, we show that infrequent energetic collisions of single ions with background gas molecules lead to pronounced heating of the entire ion ensemble and a time-varying secular ensemble temperature, which manifests itself in a superstatistical time-averaged velocity distribution of the ions. The effect of this finding on the experimental determination of ion temperatures and rate constants for cold chemical reactions is discussed.

  3. Molecular recognition of organic ammonium ions in solution using synthetic receptors

    PubMed Central

    Späth, Andreas

    2010-01-01

    Summary Ammonium ions are ubiquitous in chemistry and molecular biology. Considerable efforts have been undertaken to develop synthetic receptors for their selective molecular recognition. The type of host compounds for organic ammonium ion binding span a wide range from crown ethers to calixarenes to metal complexes. Typical intermolecular interactions are hydrogen bonds, electrostatic and cation–π interactions, hydrophobic interactions or reversible covalent bond formation. In this review we discuss the different classes of synthetic receptors for organic ammonium ion recognition and illustrate the scope and limitations of each class with selected examples from the recent literature. The molecular recognition of ammonium ions in amino acids is included and the enantioselective binding of chiral ammonium ions by synthetic receptors is also covered. In our conclusion we compare the strengths and weaknesses of the different types of ammonium ion receptors which may help to select the best approach for specific applications. PMID:20502608

  4. Interaction of monovalent ions with the water liquid-vapor interface - A molecular dynamics study

    NASA Technical Reports Server (NTRS)

    Wilson, Michael A.; Pohorille, Andrew

    1991-01-01

    Results of molecular dynamics calculations are presented for a series of ions at infinite dilution near the water liquid-vapor interface. The free energies of ion transfer from the bulk to the interface are discussed, as are the accompanying changes of water structure at the surface and ion mobilities as a function of their proximity to the interface. It is shown that simple dielectric models do not provide an accurate description of ions at the water surface. The results of the study should be useful in the development of better models incorporating the shape and molecular structure of the interface.

  5. Hybrid molecular ions emitted from CO-NH3 ice bombarded by fission fragments

    NASA Astrophysics Data System (ADS)

    Martinez, R.; Ponciano, C. R.; Farenzena, L. S.; Iza, P.; Homem, M. G. Pe; Naves de Brito, A.; da Silveira, E. F.; Wien, K.

    2007-05-01

    CO-NH3 ice at 25 K is bombarded by 65 MeV fission fragments and the emitted secondary ions are analyzed by time-of-flight mass spectrometry. The yields of the specific ion species (those formed only from CO or from NH3 molecules) and of the hybrid ion species (formed from both CO and NH3 molecules) are determined as a function of the ice temperature. The time-temperature dependence of desorption yields has been used for secondary ion identification because its behavior characterizes the ion's origin around the sublimation temperature of CO ice (~30 K). The mass spectrum of positive ions measured before CO sublimation is decomposed into three spectra corresponding to CO specific ions, NH3 specific ions and hybrid molecular ions, respectively. The observed spectrum after CO sublimation is very similar to that of a pure NH3 specific spectrum. The total yield of all positive hybrid molecular ions over 600 u mass range is found to be about 2 ions/impact: 20% of this is attributed to N and NH3 containing ions and 80% are ions having the CnOmHl+ structure. The ions Cnions is about 20 times lower than that of positive ions, the most abundant species being the cyanide ion CN-. Observation of cluster ions based on (HCN)n indicates the formation of hydrogen cyanide.

  6. Non-destructive state detection for quantum logic spectroscopy of molecular ions.

    PubMed

    Wolf, Fabian; Wan, Yong; Heip, Jan C; Gebert, Florian; Shi, Chunyan; Schmidt, Piet O

    2016-02-25

    Precision laser spectroscopy of cold and trapped molecular ions is a powerful tool in fundamental physics--used, for example, in determining fundamental constants, testing for their possible variation in the laboratory, and searching for a possible electric dipole moment of the electron. However, the absence of cycling transitions in molecules poses a challenge for direct laser cooling of the ions, and for controlling and detecting their quantum states. Previously used state-detection techniques based on photodissociation or chemical reactions are destructive and therefore inefficient, restricting the achievable resolution in laser spectroscopy. Here, we experimentally demonstrate non-destructive detection of the quantum state of a single trapped molecular ion through its strong Coulomb coupling to a well controlled, co-trapped atomic ion. An algorithm based on a state-dependent optical dipole force changes the internal state of the atom according to the internal state of the molecule. We show that individual quantum states in the molecular ion can be distinguished by the strength of their coupling to the optical dipole force. We also observe quantum jumps (induced by black-body radiation) between rotational states of a single molecular ion. Using the detuning dependence of the state-detection signal, we implement a variant of quantum logic spectroscopy of a molecular resonance. Our state-detection technique is relevant to a wide range of molecular ions, and could be applied to state-controlled quantum chemistry and to spectroscopic investigations of molecules that serve as probes for interstellar clouds. PMID:26855427

  7. Formation and fragmentation of quadruply charged molecular ions by intense femtosecond laser pulses.

    PubMed

    Yatsuhashi, Tomoyuki; Nakashima, Nobuaki

    2010-07-22

    We investigated the formation and fragmentation of multiply charged molecular ions of several aromatic molecules by intense nonresonant femtosecond laser pulses of 1.4 mum with a 130 fs pulse duration (up to 2 x 10(14) W cm(-2)). Quadruply charged states were produced for 2,3-benzofluorene and triphenylene molecular ion in large abundance, whereas naphthalene and 1,1'-binaphthyl resulted only in up to triply charged molecular ions. The laser wavelength was nonresonant with regard to the electronic transitions of the neutral molecules, and the degree of fragmentation was strongly correlated with the absorption of the singly charged cation radical. Little fragmentation was observed for naphthalene (off-resonant with cation), whereas heavy fragmentation was observed in the case of 1,1'-binaphthyl (resonant with cation). The degree of H(2) (2H) and 2H(2) (4H) elimination from molecular ions increased as the charge states increased in all the molecules examined. A striking difference was found between triply and quadruply charged 2,3-benzofluorene: significant suppression of molecular ions with loss of odd number of hydrogen was observed in the quadruply charged ions. The Coulomb explosion of protons in the quadruply charged state and succeeding fragmentation resulted in the formation of triply charged molecular ions with an odd number of hydrogens. The hydrogen elimination mechanism in the highly charged state is discussed. PMID:20578764

  8. Heavy atom nitroxyl radicals. VI. The electronic spectrum of jet-cooled H2PO, the prototypical phosphoryl free radical

    NASA Astrophysics Data System (ADS)

    Gharaibeh, Mohammed A.; Clouthier, Dennis J.; Tarroni, Riccardo

    2011-12-01

    The previously unknown electronic spectrum of the H2PO free radical has been identified in the 407-337 nm region using a combination of laser-induced fluorescence and single vibronic level emission spectroscopy. High level ab initio predictions of the properties of the ground and first two excited doublet states were used to identify the spectral region in which to search for the electronic transition and were used to aid in the analysis of the data. The band system is assigned as the {tilde B}2A'-{tilde X}2A' electronic transition which involves promotion of an electron from the π to the π* molecular orbital. The excited state r0 molecular structure was determined by rotational analysis of high resolution LIF spectra to be r(PO) = 1.6710(2) Å, r(PH) = 1.4280(6) Å, θ(HPO) = 105.68(7)°, θ(HPH) = 93.3(2)°, and the out-of-plane angle = 66.8(2)°. The structural changes on electronic excitation, which include substantial increases in the PO bond length and out-of-plane angle, are as expected based on molecular orbital theory and our previous studies of the isoelectronic H2AsO, Cl2PS, and F2PS free radicals.

  9. ION AND MOLECULE SENSORS USING MOLECULAR RECOGNITION IN LUMINESCENT, CONDUCTIVE POLYMERS

    EPA Science Inventory

    This program integrates three individual, highly interactive projects that will use molecular recognition strategies to develop sensor technology based on luminescent, conductive polymers that contain sites for binding specific molecules or ions in the presence of related molecul...

  10. The molecular motion of bovine serum albumin under physiological conditions is ion specific.

    PubMed

    Medda, Luca; Monduzzi, Maura; Salis, Andrea

    2015-04-18

    Specific ion effects on the Brownian molecular motion of BSA protein under physiological conditions are investigated. New useful insights into Hofmeister phenomena related to electrolyte-protein interactions are presented. PMID:25782536

  11. Efficient rotational cooling of Coulomb-crystallized molecular ions by a helium buffer gas.

    PubMed

    Hansen, A K; Versolato, O O; Kłosowski, L; Kristensen, S B; Gingell, A; Schwarz, M; Windberger, A; Ullrich, J; López-Urrutia, J R Crespo; Drewsen, M

    2014-04-01

    The preparation of cold molecules is of great importance in many contexts, such as fundamental physics investigations, high-resolution spectroscopy of complex molecules, cold chemistry and astrochemistry. One versatile and widely applied method to cool molecules is helium buffer-gas cooling in either a supersonic beam expansion or a cryogenic trap environment. Another more recent method applicable to trapped molecular ions relies on sympathetic translational cooling, through collisional interactions with co-trapped, laser-cooled atomic ions, into spatially ordered structures called Coulomb crystals, combined with laser-controlled internal-state preparation. Here we present experimental results on helium buffer-gas cooling of the rotational degrees of freedom of MgH(+) molecular ions, which have been trapped and sympathetically cooled in a cryogenic linear radio-frequency quadrupole trap. With helium collision rates of only about ten per second--that is, four to five orders of magnitude lower than in typical buffer-gas cooling settings--we have cooled a single molecular ion to a rotational temperature of 7.5(+0.9)(-0.7) kelvin, the lowest such temperature so far measured. In addition, by varying the shape of, or the number of atomic and molecular ions in, larger Coulomb crystals, or both, we have tuned the effective rotational temperature from about 7 kelvin to about 60 kelvin by changing the translational micromotion energy of the ions. The extremely low helium collision rate may allow for sympathetic sideband cooling of single molecular ions, and eventually make quantum-logic spectroscopy of buffer-gas-cooled molecular ions feasible. Furthermore, application of the present cooling scheme to complex molecular ions should enable single- or few-state manipulations of individual molecules of biological interest. PMID:24670662

  12. Isomer discrimination of PAHs formed in sooting flames by jet-cooled laser-induced fluorescence: application to the measurement of pyrene and fluoranthene

    NASA Astrophysics Data System (ADS)

    Mouton, Thomas; Mercier, Xavier; Desgroux, Pascale

    2016-05-01

    Jet-cooled laser-induced fluorescence is a spectroscopic method, specifically developed for the study of PAHs formed in flames. This technique has already been used to measure different aromatic species in sooting low-pressure methane flames such as benzene, naphthalene, and pyrene. The use of the LIF technique to excite PAHs drastically cooled down inside a supersonic jet offers the possibility to get selective and quantitative profiles of PAHs sampled from sooting flames. In this paper, we demonstrate the ability of this experimental method to separate the contribution of two mass isomers generated in sooting flames which are the pyrene and the fluoranthene. The selectivity of the method is demonstrated by studying the spectral properties of these species. The method is then applied to the measurement of both these species in two sooting flames with different equivalence ratios and stabilized at 200 torr (26.65 kPa). The sensitivity of the technique has been found to reach a few ppb in the case of fluoranthene measurements.

  13. An experimental and theoretical study of the A˜ 2A″Π -X˜ 2A' band system of the jet-cooled HBBr/DBBr free radical

    NASA Astrophysics Data System (ADS)

    Gharaibeh, Mohammed; Clouthier, Dennis J.; Tarroni, Riccardo

    2016-06-01

    The electronic spectra of the HBBr and DBBr free radicals have been studied in depth. These species were prepared in a pulsed electric discharge jet using a precursor mixture of BBr3 vapor and H2 or D2 in high pressure argon. Transitions to the electronic excited state of the jet-cooled radicals were probed with laser-induced fluorescence and the ground state energy levels were measured from the single vibronic level emission spectra. HBBr has an extensive band system in the red which involves a linear-bent transition between the two Renner-Teller components of what would be a 2Π state at linearity. We have used high level ab initio theory to calculate potential energy surfaces for the bent 2A' ground state and the linear A˜ 2A″Π excited state and we have determined the ro-vibronic energy levels variationally, including spin orbit effects. The correspondence between the computed and experimentally observed transition frequencies, upper state level symmetries, and H and B isotope shifts was used to make reliable assignments. We have shown that the ground state barriers to linearity, which range from 10 000 cm-1 in HBF to 2700 cm-1 in BH2, are inversely related to the energy of the first excited 2Σ (2A') electronic state. This suggests that a vibronic coupling mechanism is responsible for the nonlinear equilibrium geometries of the ground states of the HBX free radicals.

  14. An experimental and theoretical study of the Ã(2)A(″)Π-X̃(2)A(') band system of the jet-cooled HBBr/DBBr free radical.

    PubMed

    Gharaibeh, Mohammed; Clouthier, Dennis J; Tarroni, Riccardo

    2016-06-21

    The electronic spectra of the HBBr and DBBr free radicals have been studied in depth. These species were prepared in a pulsed electric discharge jet using a precursor mixture of BBr3 vapor and H2 or D2 in high pressure argon. Transitions to the electronic excited state of the jet-cooled radicals were probed with laser-induced fluorescence and the ground state energy levels were measured from the single vibronic level emission spectra. HBBr has an extensive band system in the red which involves a linear-bent transition between the two Renner-Teller components of what would be a (2)Π state at linearity. We have used high level ab initio theory to calculate potential energy surfaces for the bent (2)A' ground state and the linear Ã(2)A(″)Π excited state and we have determined the ro-vibronic energy levels variationally, including spin orbit effects. The correspondence between the computed and experimentally observed transition frequencies, upper state level symmetries, and H and B isotope shifts was used to make reliable assignments. We have shown that the ground state barriers to linearity, which range from 10 000 cm(-1) in HBF to 2700 cm(-1) in BH2, are inversely related to the energy of the first excited (2)Σ ((2)A') electronic state. This suggests that a vibronic coupling mechanism is responsible for the nonlinear equilibrium geometries of the ground states of the HBX free radicals. PMID:27334164

  15. Generalized Langevin models of molecular dynamics simulations with applications to ion channels

    NASA Astrophysics Data System (ADS)

    Gordon, Dan; Krishnamurthy, Vikram; Chung, Shin-Ho

    2009-10-01

    We present a new methodology, which combines molecular dynamics and stochastic dynamics, for modeling the permeation of ions across biological ion channels. Using molecular dynamics, a free energy profile is determined for the ion(s) in the channel, and the distribution of random and frictional forces is measured over discrete segments of the ion channel. The parameters thus determined are used in stochastic dynamics simulations based on the nonlinear generalized Langevin equation. We first provide the theoretical basis of this procedure, which we refer to as "distributional molecular dynamics," and detail the methods for estimating the parameters from molecular dynamics to be used in stochastic dynamics. We test the technique by applying it to study the dynamics of ion permeation across the gramicidin pore. Given the known difficulty in modeling the conduction of ions in gramicidin using classical molecular dynamics, there is a degree of uncertainty regarding the validity of the MD-derived potential of mean force (PMF) for gramicidin. Using our techniques and systematically changing the PMF, we are able to reverse engineer a modified PMF which gives a current-voltage curve closely matching experimental results.

  16. Molecular microenvironments: Solvent interactions with nucleic acid bases and ions

    NASA Technical Reports Server (NTRS)

    Macelroy, R. D.; Pohorille, A.

    1986-01-01

    The possibility of reconstructing plausible sequences of events in prebiotic molecular evolution is limited by the lack of fossil remains. However, with hindsight, one goal of molecular evolution was obvious: the development of molecular systems that became constituents of living systems. By understanding the interactions among molecules that are likely to have been present in the prebiotic environment, and that could have served as components in protobiotic molecular systems, plausible evolutionary sequences can be suggested. When stable aggregations of molecules form, a net decrease in free energy is observed in the system. Such changes occur when solvent molecules interact among themselves, as well as when they interact with organic species. A significant decrease in free energy, in systems of solvent and organic molecules, is due to entropy changes in the solvent. Entropy-driven interactioins played a major role in the organization of prebiotic systems, and understanding the energetics of them is essential to understanding molecular evolution.

  17. Method and source for producing a high concentration of positively charged molecular hydrogen or deuterium ions

    DOEpatents

    Ehlers, Kenneth W.; Leung, Ka-Ngo

    1988-01-01

    A high concentration of positive molecular ions of hydrogen or deuterium gas is extracted from a positive ion source having a short path length of extracted ions, relative to the mean free path of the gas molecules, to minimize the production of other ion species by collision between the positive ions and gas molecules. The ion source has arrays of permanent magnets to produce a multi-cusp magnetic field in regions remote from the plasma grid and the electron emitters, for largely confining the plasma to the space therebetween. The ion source has a chamber which is short in length, relative to its transverse dimensions, and the electron emitters are at an even shorter distance from the plasma grid, which contains one or more extraction apertures.

  18. ARTEMIS observations of terrestrial ionospheric molecular ion outflow at the Moon

    NASA Astrophysics Data System (ADS)

    Poppe, A. R.; Fillingim, M. O.; Halekas, J. S.; Raeder, J.; Angelopoulos, V.

    2016-07-01

    The Acceleration, Reconnection, Turbulence, and Electrodynamics of the Moon's Interaction with the Sun (ARTEMIS) spacecraft observes outflowing molecular ionospheric ions at lunar distances in the terrestrial magnetotail. The heavy ion fluxes are observed during geomagnetically disturbed times and consist of mainly molecular species (N2+, NO+, and O2+, approximately masses 28-32 amu) on the order of 105-106 cm-2 s-1 at nearly identical velocities as concurrently present protons. By performing backward particle tracing in time-dependent electromagnetic fields from the magnetohydrodynamic Open Global Geospace Circulation Model of the terrestrial magnetosphere, we show that the ions escape the inner magnetosphere through magnetopause shadowing near noon and are subsequently accelerated to common velocities down the low-latitude boundary layer to lunar distances. At the Moon, the observed molecular ion outflow can sputter significant fluxes of neutral species into the lunar exosphere while also delivering nitrogen and oxygen to the lunar volatile inventory.

  19. Infrared laser spectroscopy of jet-cooled carbon clusters: the nu 5 band of linear C9

    NASA Technical Reports Server (NTRS)

    Van Orden, A.; Provencal, R. A.; Keutsch, F. N.; Saykally, R. J.

    1996-01-01

    The nu 5 antisymmetric stretching vibration of 1 sigma+g C9 has been observed using direct infrared diode laser absorption spectroscopy of a pulsed supersonic cluster beam. Twenty-eight rovibrational transitions measured in the region of 2079-2081 cm-1 were assigned to this band. A combined least squares fit of these transitions with previously reported nu 6 transitions yielded the following molecular constants for the nu 5 band: nu 0 = 2 079.673 58(17) cm-1, B"= 0.014 321 4(10) cm-1, and B'=0.014 288 9(10) cm-1. The IR intensity of the nu 5 band relative to nu 6 was found to be 0.108 +/- 0.006. Theoretical predictions for the relative intensities vary widely depending upon the level of theory employed, and the experimental value reported here is in reasonable agreement only with the result obtained from the most sophisticated ab initio calculation considered (CCSD).

  20. Determination of molecular-ion structures through the use of accelerated beams

    SciTech Connect

    Gemmell, D.S.

    1987-01-01

    In this talk we report on recent research on molecular-ion structures using fast molecular-ion beams provided by Argonne's 5-MV Dynamitron accelerator. The method has become known as the ''Coulomb-explosion'' technique. When molecular-ion projectiles travelling at velocities of a few percent of the velocity of light strike a foil, the electrons that bind the molecular projectiles are almost always totally stripped off within the first few Angstroms of penetration into the solid target. This leaves a cluster of bare (or nearly bare) nuclei which separate rapidly as a result of their mutual Coulomb repulsion. This violent dissociation process in which the initial electrostatic potential energy is converted into kinetic energy of relative motion in the center-of-mass, has been termed a ''Coulomb explosion.'' 4 refs., 2 figs.

  1. Studies on Molecular and Ion Transport in Silicalite Membranes and Applications as Ion Separator for Redox Flow Battery

    NASA Astrophysics Data System (ADS)

    Yang, Ruidong

    Microporous zeolite membranes have been widely studied for molecular separations based on size exclusion or preferential adsorption-diffusion mechanisms. The MFI-type zeolite membranes were also demonstrated for brine water desalination by molecular sieving effect. In this research, the pure silica MFI-type zeolite (i.e. silicalite) membrane has been for the first time demonstrated for selective permeation of hydrated proton (i.e. H3O+) in acidic electrolyte solutions. The silicalite membrane allows for permeation of H 3O+ ions, but is inaccessible to the large hydrated multivalent vanadium ions due to steric effect. The silicalite membrane has been further demonstrated as an effective ion separator in the all-vanadium redox flow battery (RFB).The silicalite is nonionic and its proton conductivity relies on the electric field-driven H3O+ transport through the sub nanometer-sized pores under the RFB operation conditions. The silicalite membrane displayed a significantly reduced self-discharge rate because of its high proton-to-vanadium ion transport selectivity. However, the nonionic nature of the silicalite membrane and very small diffusion channel size render low proton conductivity and is therefore inefficient as ion exchange membranes (IEMs) for practical applications. The proton transport efficiency may be improved by reducing the membrane thickness. However, the zeolite thin films are extremely fragile and must be supported on mechanically strong and rigid porous substrates. In this work, silicalite-Nafion composite membranes were synthesized to achieve a colloidal silicalite skin on the Nafion thin film base. The "colloidal zeolite-ionic polymer" layered composite membrane combines the advantages of high proton-selectivity of the zeolite layer and the mechanical flexibility and low proton transport resistance of the ionic polymer membrane. The composite membrane exhibited higher proton/vanadium ion separation selectivity and lower electrical resistance than

  2. Out-of-plane low-frequency vibrations and nonradiative decay in the 1ππ* state of jet-cooled 5-methylcytosine.

    PubMed

    Trachsel, Maria A; Lobsiger, Simon; Leutwyler, Samuel

    2012-09-13

    We investigate the UV vibronic spectrum and excited-state nonradiative processes of jet-cooled 5-methylcytosine (5MCyt) using two-color resonant two-photon ionization spectroscopy at 0.3 and 0.05 cm(–1) resolution. In contrast to cytosine, which shows only five bands above its electronic origin, the lowest electronic transition of 5MCyt exhibits about 25 low-frequency vibronic bands that extend to 0(0)(0) + 450 cm(–1), allowing to extract detailed information on the excited-state electronic and nuclear structure. Most bands are overtones and combinations of the out-of-plane vibrations ν'(1), ν'(2), and ν'(3). Their large intensities reflect butterfly-, boat-, and twist-deformations of the 5MCyt framework upon electronic excitation. From the rotational contours of the 0(0)(0), 1(0)(2), 2(0)(2), and 3(0)(2) bands, the transition is found to be polarized along the in-plane a/b axes, characteristic of a (1)ππ* transition. Approximate second-order coupled-cluster (CC2) and time-dependent B3LYP calculations both predict that 5MCyt undergoes an out-of-plane deformation in its (1)ππ* (S(2)) state but both methods overestimate the out-of-plane ν'(1), ν'(2), and ν'(3) vibrational frequencies by a factor of 3–5. The TD-B3LYP (1)ππ* transition dipole moment direction is 10%:90% a:b, in good agreement with experiment. From the Lorentzian line shape contributions needed to fit the rotational contours, a lower limit to the 5MCyt (1)ππ* state lifetime at the 0(0)(0), 1(0)(2), 2(0)(2), and 3(0)(2) bands is determined as τ ≥ 30 ps. These values are in stark contrast to the ultrafast (picosecond) lifetimes measured for jet-cooled cytosine by femtosecond pump–probe techniques. They also confirm the observation from the R2PI spectrum that 5-methylation of cytosine increases its excited-state lifetime. The higher out-of-plane overtone and combination bands disappear from the spectrum by ~460 cm(–1), signaling the onset of lifetimes τ < 0.5 ps, induced by

  3. Jet-Cooled Cavity Ring-Down Spectroscopy of the ~a ^2E^"-~X ^2A_2^' Vibronic Transition of NO_3

    NASA Astrophysics Data System (ADS)

    Chen, Ming-Wei; Just, Gabriel M. P.; Codd, Terrance; Miller, Terry A.

    2010-06-01

    The three energetically lowest electronic states (~X 2A2^', ~A 2E^", and ~B 2E^') of NO_3 are strongly coupled by vibronic interactions and have been treated in considerable detail theoretically. Corresponding experimental characterization of the interaction is much less detailed. Previous experimental results primarily consist of IR measurements of vibrational transitions in the ground state. In addition, the electronically forbidden ~A-~X transition has been observed in ambient temperature CRDS studies. A slit-jet nozzle with a high voltage pulsed discharge has been applied to produce the NO_3 radical by dissociating the N-O bond of N_2O_5, and the jet-cooled NO_3 CRDS absorption spectrum has been successfully observed with a high-resolution laser source (Δν≈250MHz, intrinsic resolution considering the instrumental linewidth and the residual Doppler broadening in the jet). The 4^1_0 band (parallel band) shows complex rotational structure which is presently being analyzed. The 2^1_0 band has also been measured as an example of a perpendicular band. Besides the ν_2 and ν_4 vibronic bands, the vibronically forbidden origin band (0^0_0 band) has been recorded under the same experimental conditions. The weakly observed ~A-~X origin band is likely either a magnetic dipole or an electric quardrupole transition. J. F. Stanton, J. Chem. Phys., 126, 134309 (2007) K. Kawaguchi, E. Hirota, T. Ishiwata, and I. Tanaka, J. Chem. Phys., 93, 951 (1990) K. Kawaguchi, T. Ishiwata, E. Hirota, and I. Tanaka, Chem. Phys., 231, 193 (1998) A. Deev, J. Sommar, and M. Okumura, J. Chem. Phys., 122, 224305 (2005) E. Hirota, T. Ishiwata, K. Kawaguchi, M. Fujitake, N. Ohashi, I. Tanaka, J. Chem. Phys., 107, 2829 (1997)

  4. Jet-cooled infrared spectroscopy in slit supersonic discharges: symmetric and antisymmetric CH2 stretching modes of fluoromethyl (CH2F) radical.

    PubMed

    Whitney, Erin S; Dong, Feng; Nesbitt, David J

    2006-08-01

    The combination of shot noise-limited direct absorption spectroscopy with long-path-length slit supersonic discharges has been used to obtain first high-resolution infrared spectra for jet-cooled CH2F radicals in the symmetric (nu1) and antisymmetric (nu5) CH2 stretching modes. Spectral assignment has yielded refined lower- and upper-state rotational constants and fine-structure parameters from least-squares fits to the sub-Doppler line shapes for individual transitions. The rotational constants provide indications of large amplitude vibrational averaging over a low-barrier double minimum inversion-bending potential. This behavior is confirmed by high-level coupled cluster singles/doubles/triples calculations extrapolated to the complete basis set limit and adiabatically corrected for zero point energy. The calculations predict a nonplanar equilibrium structure (theta approximately 29 degrees, where theta is defined to be 180 degrees minus the angle between the C-F bond and the CH2 plane) with a 132 cm(-1) barrier to planarity and a vibrational bend frequency (nu(bend) approximately 276 cm(-1)), in good agreement with previous microwave estimates (nu(bend) = 300 (30) cm(-1)) by Hirota and co-workers [Y. Endo et al., J. Chem. Phys. 79, 1605 (1983)]. The nearly 2:1 ratio of absorption intensities for the symmetric versus antisymmetric bands is in good agreement with density functional theory calculations, but in sixfold contrast with simple local mode CH2 bond dipole predictions of 1:3. This discrepancy arises from a surprisingly strong dependence of the symmetric stretch intensity on the inversion bend angle and provides further experimental support for a nonplanar equilibrium structure. PMID:16942210

  5. Probabilistic rotational state preparation of a single molecular ion though consecutive partial projection measurements

    NASA Astrophysics Data System (ADS)

    Drewsen, Michael

    2016-05-01

    Fully quantum state prepared molecular ions are of interest for a wide range of research fields, including ultra-cold chemistry, ultra-high resolution spectroscopy for test of fundamental physics, and quantum information science. Cooling of the translational degrees of freedom of trapped molecular ions into the millikelvin range has become routine through Coulomb interactions with simultaneously trapped and Doppler laser-cooled atomic ions, and recently it has even become possible to prepare a single molecular ion in its absolute ground state with respect to its quantized motion in the external trapping potential. With respect to the internal rovibrational degrees of freedom, significant progress towards single quantum state preparation has as well recently been realized by a series of complementary methods. In the talk, a novel method for probabilistic rotational state preparation of polar molecular ions based on consecutive partial projection measurements will be discussed. Results of state preparation of vibrational cold single MgH+ ions in the rotational ground or first excited state with maximum likelihood estimated populations of 0.98 and 0.95, respectively, will be presented.

  6. Experiments on Interactions of Electrons with Molecular Ions in Fusion and Astrophysical Plasmas

    NASA Astrophysics Data System (ADS)

    Bannister, M. E.; Aliabadi, H.; Bahati, E. M.; Fogle, M. R.; Krstić, P.; Vane, C. R.; Ehlerding, A.; Geppert, W.; Hellberg, F.; Zhaunerchyk, V.; Larsson, M.; Thomas, R. D.

    2007-08-01

    Through beam-beam experiments at the Multicharged Ion Research Facility (MIRF) at Oak Ridge National Laboratory (ORNL) and at the CRYRING heavy ion storage ring at Stockholm University, we are seeking to formulate a more complete picture of electron-impact dissociation of molecular ions. These inelastic collisions play important roles in many low temperature plasmas such as in divertors of fusion devices and in astrophysical environments. An electron-ion crossed beams experiment at ORNL investigates the dissociative excitation and dissociative ionization of molecular ions from a few eV up to 100 eV. Measurements on dissociative recombination (DR) experiments are made at CRYRING, where chemical branching fractions and fragmentation dynamics are studied. Taking advantage of a 250-kV acceleration platform at the MIRF, a merged electron-ion beams energy loss apparatus is employed to study DR down to zero energy. Recent results on the dissociation of molecular ions of importance in fusion and astrophysics are presented.

  7. Molecular dynamics simulations of swift heavy ion induced defect recovery in SiC

    SciTech Connect

    Backman, Marie; Toulemonde, Marcel; Pakarinen, Olli H; Juslin, Niklas; Djurabekova, Flyura; Nordlund, Kai; Debelle, Aurelien; Weber, William J

    2013-01-01

    Swift heavy ions induce a high density of electronic excitations that can cause the formation of amorphous ion tracks in insulators. No ion tracks have been observed in the semiconductor SiC, but recent experimental work suggests that irradiation damaged SiC can undergo defect recovery under swift heavy ion irradiation. It is believed that local heating of the lattice due to the electronic energy deposition can anneal, and thereby recover, some of the disordered structure. We simulate the local heating due to the ions by the inelastic thermal spike model and perform molecular dynamics simulations of dierent model damage states to study the defect recovery on an atomistic level. We find significant recovery of point defects and a disordered layer, as well as recrystallization at the amorphous-to-crystalline interface of an amorphous layer. The simulation results support the swift heavy ion annealing hypothesis.Swift heavy ions induce a high density of electronic excitations that can cause the formation of amorphous ion tracks in insulators. No ion tracks have been observed in the semiconductor SiC, but recent experimental work suggests that irradiation damaged SiC can undergo defect recovery under swift heavy ion irradiation. It is believed that local heating of the lattice due to the electronic energy deposition can anneal, and thereby recover, some of the disordered structure. We simulate the local heating due to the ions by the inelastic thermal spike model and perform molecular dynamics simulations of dierent model damage states to study the defect recovery on an atomistic level. We find significant recovery of point defects and a disordered layer, as well as recrystallization at the amorphous-to-crystalline interface of an amorphous layer. The simulation results support the swift heavy ion annealing hypothesis.

  8. Ion Channels in Plant Bioenergetic Organelles, Chloroplasts and Mitochondria: From Molecular Identification to Function.

    PubMed

    Carraretto, Luca; Teardo, Enrico; Checchetto, Vanessa; Finazzi, Giovanni; Uozumi, Nobuyuki; Szabo, Ildiko

    2016-03-01

    Recent technical advances in electrophysiological measurements, organelle-targeted fluorescence imaging, and organelle proteomics have pushed the research of ion transport a step forward in the case of the plant bioenergetic organelles, chloroplasts and mitochondria, leading to the molecular identification and functional characterization of several ion transport systems in recent years. Here we focus on channels that mediate relatively high-rate ion and water flux and summarize the current knowledge in this field, focusing on targeting mechanisms, proteomics, electrophysiology, and physiological function. In addition, since chloroplasts evolved from a cyanobacterial ancestor, we give an overview of the information available about cyanobacterial ion channels and discuss the evolutionary origin of chloroplast channels. The recent molecular identification of some of these ion channels allowed their physiological functions to be studied using genetically modified Arabidopsis plants and cyanobacteria. The view is emerging that alteration of chloroplast and mitochondrial ion homeostasis leads to organelle dysfunction, which in turn significantly affects the energy metabolism of the whole organism. Clear-cut identification of genes encoding for channels in these organelles, however, remains a major challenge in this rapidly developing field. Multiple strategies including bioinformatics, cell biology, electrophysiology, use of organelle-targeted ion-sensitive probes, genetics, and identification of signals eliciting specific ion fluxes across organelle membranes should provide a better understanding of the physiological role of organellar channels and their contribution to signaling pathways in plants in the future. PMID:26751960

  9. Production of lanthanide molecular ion beams by fluorination technique

    NASA Astrophysics Data System (ADS)

    Roussière, B.; Deloncle, I.; Barré-Boscher, N.; Cardona, M. A.; Cheikh Mhamed, M.; Corbin, T.; Cottereau, E.; Croizet, H.; Dimitrov, B.; Essabaa, S.; Gavrilov, G.; Gottardo, A.; Goutev, N.; Guillot, J.; Hojman, D.; Lau, C.; Roccia, S.; Tusseau-Nenez, S.; Verney, D.; Yavahchova, M.; the ALTO collaboration

    2016-06-01

    Systematic off-line fluorination studies on all the stable lanthanide isotopes have been performed. The results are presented as a function of various parameters such as the target temperature, the type of ion source used (hot plasma or surface ionization) and the quantity of CF4 introduced. The first on-line measurements allowed us to determine the optimal experimental conditions for producing radioactive lanthanide isotopes.

  10. DETERMINATION OF MOLECULAR WEIGHT CITRUS PECTIN USING ION CHROMATOGRAPHY

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Objective was to investigate the use of ELS as a mass detector coupled with MALLS for determining the molecular weights of pectins and other polysaccharides under changing buffer concentrations using HPLC. This would permit the direct determination of the charge to size ratio of pectin which is imp...

  11. Molecular Interactions in 1-Ethyl-3-methylimidazolium Acetate Ion Pair: A Density Functional Study

    NASA Astrophysics Data System (ADS)

    Dhumal, Nilesh R.; Kim, Hyung J.; Kiefer, Johannes

    2009-08-01

    The density functional method is used to obtain the molecular structure, electron density topography, and vibrational frequencies of the ion pair 1-ethyl-3-methylimidazolium acetate. Different conformers are simulated on the basis of molecular interactions between the 1-ethyl-3-methylimidazolium cation and acetate anion. The lowest energy conformers exhibit strong C-H···O interionic interactions compared with other conformers. Characteristic vibrational frequencies of the ion pair and their shifts with respect to free ions are analyzed via the natural bond orbitals and difference electron density maps coupled with molecular electron density topology. Theoretically scaled vibrational frequencies are also compared with the spontaneous Raman scattering and attenuated total reflection infrared absorption measurements.

  12. Ab initio investigation of electronic properties of the magnesium hydride molecular ion.

    PubMed

    Khemiri, Noura; Dardouri, Riadh; Oujia, Brahim; Gadéa, Florent Xavier

    2013-09-12

    In this work, adiabatic potential energy curves, spectroscopic constants, dipole moments, and vibrational levels for numerous electronic states of magnesium hydride molecular ion (MgH(+)) are computed. These properties are determined by the use of an ab initio method involving a nonempirical pseudopotential for the magnesium core (Mg), the core polarization potential (CPP), the l-dependent cutoff functions and the full valence configuration interaction (FCI). The molecular ion is thus treated as a two-electron system. Our calculations on the MgH(+) molecular ion extend previous theoretical works to numerous electronic excited states in the various symmetries. A good agreement with the available theoretical and experimental works is obtained for the spectroscopic constants, the adiabatic potential energy curves, and the dipole moments for the lowest states of MgH(+). PMID:23944679

  13. Measurement of the density profile of pure and seeded molecular beams by femtosecond ion imaging.

    PubMed

    Meng, Congsen; Janssen, Maurice H M

    2015-02-01

    Here, we report on femtosecond ion imaging experiments to measure the density profile of a pulsed supersonic molecular beam. Ion images are measured for both a molecular beam and bulk gas under identical experimental conditions via femtosecond multiphoton ionization of Xe atoms. We report the density profile of the molecular beam, and the measured absolute density is compared with theoretical calculations of the centre line beam density. Subsequently, we discuss reasons accounting for the differences between measurements and calculations and propose that strong skimmer interference is the most probable cause for the differences. Furthermore, we report on experiments measuring the centre line density of seeded supersonic beams. The femtosecond ion images show that seeding the heavy Xe atom at low relative seed fractions (1%-10%) in a light carrier gas like Ne results in strong relative enhancements of up to two orders of magnitude. PMID:25725826

  14. Measurement of the density profile of pure and seeded molecular beams by femtosecond ion imaging

    SciTech Connect

    Meng, Congsen; Janssen, Maurice H. M.

    2015-02-15

    Here, we report on femtosecond ion imaging experiments to measure the density profile of a pulsed supersonic molecular beam. Ion images are measured for both a molecular beam and bulk gas under identical experimental conditions via femtosecond multiphoton ionization of Xe atoms. We report the density profile of the molecular beam, and the measured absolute density is compared with theoretical calculations of the centre line beam density. Subsequently, we discuss reasons accounting for the differences between measurements and calculations and propose that strong skimmer interference is the most probable cause for the differences. Furthermore, we report on experiments measuring the centre line density of seeded supersonic beams. The femtosecond ion images show that seeding the heavy Xe atom at low relative seed fractions (1%-10%) in a light carrier gas like Ne results in strong relative enhancements of up to two orders of magnitude.

  15. Molecular hydrogen ion elimination from alkyl iodides under strong laser beam irradiation

    NASA Astrophysics Data System (ADS)

    Kosmidis, C.; Kaziannis, S.; Siozos, P.; Lyras, A.; Robson, L.; Ledingham, K. W. D.; McKenna, P.; Jaroszynski, D. A.

    2006-01-01

    The elimination of H2+ from alkyl iodides under strong (up to 5 × 1015 W cm-2) laser irradiation is studied by means of time-of-flight mass spectrometry. The study has been performed by using 60 fs ([lambda] = 800 nm) and 35 ps ([lambda] = 1064, 532, 355 and 266 nm) laser pulses. It is concluded that the H2+ ions are ejected from ionic states via Coulomb explosion processes. The molecular rearrangement leading to H2+ formation is attributed to a tunneling process through a H transfer barrier. For the case of methyl iodide, about 10% of the doubly charged parent ions undergo molecular rearrangement. From a comparison of the H2+/H+ ion yield ratio of the studied molecules, it turns out that the H2+ formation from H atoms bonded to a terminal carbon atom is more efficient than that arising from H atoms bonded to central C atoms of the molecular chain.

  16. Spatial decomposition of molecular ions within 3D atom probe reconstructions.

    PubMed

    Breen, Andrew; Moody, Michael P; Gault, Baptiste; Ceguerra, Anna V; Xie, Kelvin Y; Du, Sichao; Ringer, Simon P

    2013-09-01

    Two methods for separating the constituent atoms of molecular ions within atom probe tomography reconstructions are presented. The Gaussian Separation Method efficiently deconvolutes molecular ions containing two constituent atoms and is tested on simulated data before being applied to an experimental HSLA steel dataset containing NbN. The Delaunay Separation Method extends separation to larger complex ions and is also tested on simulated data before being applied to an experimental GaAs dataset containing many large (>3 atoms) complex ions. First nearest neighbour (1NN) distributions and images of the reconstruction before and after the separations are used to show the effect of the algorithms and their validity and practicality are also discussed. PMID:23522847

  17. Hydrogen molecular ions: new schemes for metrology and fundamental physics tests

    NASA Astrophysics Data System (ADS)

    Karr, Jean-Philippe; Patra, Sayan; Koelemeij, Jeroen C. J.; Heinrich, Johannes; Sillitoe, Nicolas; Douillet, Albane; Hilico, Laurent

    2016-06-01

    High-accuracy spectroscopy of hydrogen molecular ions has important applications for the metrology of fundamental constants and tests of fundamental theories. Up to now, the experimental resolution has not surpassed the part-per-billion range. We discuss two methods by which it could be improved by a huge factor. Firstly, the feasibility of Doppler-free quasidegenerate two-photon spectroscopy of trapped and sympathetically cooled ensembles of HD+ ions is discussed, and it is shown that rovibrational transitions may be detected with a good signal-to-noise ratio. Secondly, the performance of a molecular quantum-logic ion clock based on a single Be+-H2 + ion pair is analyzed in detail. Such a clock could allow testing the constancy of the proton-to-electron mass ratio at the 10-17/yr level.

  18. Generation of circularly polarized attosecond pulses by intense ultrashort laser pulses from extended asymmetric molecular ions

    NASA Astrophysics Data System (ADS)

    Yuan, Kai-Jun; Bandrauk, André D.

    2011-08-01

    We present a method for generation of single circularly polarized attosecond pulses in extended asymmetric HHe2+ molecular ions. By employing an intense ultrashort circularly polarized laser pulse with intensity 4.0×1014 W/cm2, wavelength 400 nm, and duration 10 optical cycles, molecular high-order-harmonic generation (MHOHG) spectra with multiple plateaus exhibit characters of circular polarization. Using a classical laser-induced collision model, double collisions of continuum electrons first with neighboring ions and then second with parent ions are presented at a particular internuclear distance and confirmed from numerical solutions of a time-dependent Schrödinger equation. We analyze the MHOHG spectra with a Gabor time window and find that, due to the asymmetry of HHe2+, a single collision trajectory of continuum electrons with ions can produce circularly polarized harmonics, leading to single circularly polarized attosecond pulses for specific internuclear distances.

  19. Generation of circularly polarized attosecond pulses by intense ultrashort laser pulses from extended asymmetric molecular ions

    SciTech Connect

    Yuan, Kai-Jun; Bandrauk, Andre D.

    2011-08-15

    We present a method for generation of single circularly polarized attosecond pulses in extended asymmetric HHe{sup 2+} molecular ions. By employing an intense ultrashort circularly polarized laser pulse with intensity 4.0x10{sup 14} W/cm{sup 2}, wavelength 400 nm, and duration 10 optical cycles, molecular high-order-harmonic generation (MHOHG) spectra with multiple plateaus exhibit characters of circular polarization. Using a classical laser-induced collision model, double collisions of continuum electrons first with neighboring ions and then second with parent ions are presented at a particular internuclear distance and confirmed from numerical solutions of a time-dependent Schroedinger equation. We analyze the MHOHG spectra with a Gabor time window and find that, due to the asymmetry of HHe{sup 2+}, a single collision trajectory of continuum electrons with ions can produce circularly polarized harmonics, leading to single circularly polarized attosecond pulses for specific internuclear distances.

  20. Three-dimensional momentum imaging of delayed dissociation of metastable molecular ions

    NASA Astrophysics Data System (ADS)

    Malakar, Y.; Jochim, Bethany; Erdwien, Reid; Carnes, K. D.; Pearson, W. L.; Rudenko, A.; Ben-Itzhak, I.

    2016-05-01

    Coincidence three-dimensional momentum imaging has been a powerful technique in studies of molecular fragmentation following ionization by ultrashort intense laser pulses, fast ion or electron impact, etc. On occasion, the fragmentation process of the intermediate molecular ion can be delayed by a significant fraction of the flight time to the detector due to the presence of metastable states. We focus on the signatures of delayed dissociation into an ion pair observed in coincidence spectra obtained using cold target recoil ion momentum spectrometry (COLTRIMS). Moreover, we present a method for recovering the complete 3D momenta of the dissociating fragments as well as the time delay of the dissociation. Laser-induced dissociation of hydrocarbon dications, for example C2 H42+ --> H+ + C2 H3+,is used to demonstrate the method. Supported by the Chemical Sciences, Geosciences, and Biosciences Division, Office of Basic Energy Sciences, Office of Science, U. S. Department of Energy.

  1. DETERMINATION OF ELEMENTAL COMPOSITIONS FROM MASS PEAK PROFILES OF THE MOLECULAR ION (M) AND THE M + 1 AND M + 2 IONS

    EPA Science Inventory

    The relative abundances of M + 1 and M + 2 ions help to identify the elemental composition of the molecular ion (M). But scan speed, snesitiity, and resolution limitations of mass spectrometers have impeded determination of these abundances. Mass peak profiling from selected ion ...

  2. Millimeter-Wave Spectroscopic and Collisional Studies of Molecules and Molecular Ions

    NASA Astrophysics Data System (ADS)

    Pearson, John Christoffersen

    1995-01-01

    Molecular spectroscopy in the millimeter- and submillimeter-wave regions is an important tool in molecular physics. Information on molecular motions and interactions is obtained from spectroscopic studies of energy levels and collisions. This information and the data from which it is derived are essential in remote sensing of the atmosphere and the interstellar medium. Remote sensing at submillimeter wavelengths is now possible, making higher frequency and quantum number measurements of known interstellar species like water, propionitrile and ethyl alcohol necessary. Remote sensing improvements have also facilitated the need for spectral data on suspected interstellar molecules like propylene. The desire to extract quantitative information from atmospheric remote sensing has resulted in the need for a better understanding of the molecular interactions that cause pressure broadening. The use of a cold molecular ion to magnify the effects of intermolecular interactions has serious implications for pressure broadening theory. The measurement and analysis of rotational spectra of the asymmetric rotors water and propionitrile and the internal rotors propylene and ethyl alcohol are presented. These investigations provide the data and analysis necessary for astronomical observation. The ethyl alcohol investigation is the first experimental millimeter-wave study of a molecule with an asymmetric internal rotor. This study provides the data necessary for detailed theoretical modeling of this type of problem. A novel new experimental technique for generating and studying molecular ions is presented. The first temperature dependent microwave pressure broadening study of a molecular ion colliding with a neutral molecule, HCO^{+} on H_2 , is presented.

  3. Ultra-sensitive high-precision spectroscopy of a fast molecular ion beam

    SciTech Connect

    Mills, Andrew A.; Siller, Brian M.; Porambo, Michael W.; Perera, Manori; Kreckel, Holger; McCall, Benjamin J.

    2011-12-14

    Direct spectroscopy of a fast molecular ion beam offers many advantages over competing techniques, including the generality of the approach to any molecular ion, the complete elimination of spectral confusion due to neutral molecules, and the mass identification of individual spectral lines. The major challenge is the intrinsic weakness of absorption or dispersion signals resulting from the relatively low number density of ions in the beam. Direct spectroscopy of an ion beam was pioneered by Saykally and co-workers in the late 1980s, but has not been attempted since that time. Here, we present the design and construction of an ion beam spectrometer with several improvements over the Saykally design. The ion beam and its characterization have been improved by adopting recent advances in electrostatic optics, along with a time-of-flight mass spectrometer that can be used simultaneously with optical spectroscopy. As a proof of concept, a noise-immune cavity-enhanced optical heterodyne molecular spectroscopy (NICE-OHMS) setup with a noise equivalent absorption of {approx}2 x 10{sup -11} cm{sup -1} Hz{sup -1/2} has been used to observe several transitions of the Meinel 1-0 band of N{sub 2}{sup +} with linewidths of {approx}120 MHz. An optical frequency comb has been used for absolute frequency calibration of transition frequencies to within {approx}8 MHz. This work represents the first direct spectroscopy of an electronic transition in an ion beam, and also represents a major step toward the development of routine infrared spectroscopy of rotationally cooled molecular ions.

  4. The roles of electronic and nuclear stopping in the desorption valine negative molecular ions

    SciTech Connect

    Hunt, J.E.; Salehpour, M.; Fishel, D.L.; Tou, J.C.

    1988-01-01

    The yield of valine negative molecular ions has been measured as a function of Xe/sup +/, Kr/sup +/, and Ar/sup +/ primary ion velocity. The electronic and nuclear stopping powers are comparable in magnitude and opposite in slope in the experimental velocity region. The yield data are explained in terms of electronic stopping power alone, with no contribution from nuclear stopping power within the experimental error. Low molecular weight atomic species are found to be best described by a nuclear stopping power related process. 18 refs., 3 figs.

  5. Double-modulation spectroscopy of molecular ions - Eliminating the background in velocity-modulation spectroscopy

    NASA Technical Reports Server (NTRS)

    Lan, Guang; Tholl, Hans Dieter; Farley, John W.

    1991-01-01

    Velocity-modulation spectroscopy is an established technique for performing laser absorption spectroscopy of molecular ions in a discharge. However, such experiments are often plagued by a coherent background signal arising from emission from the discharge or from electronic pickup. Fluctuations in the background can obscure the desired signal. A simple technique using amplitude modulation of the laser and two lock-in amplifiers in series to detect the signal is demonstrated. The background and background fluctuations are thereby eliminated, facilitating the detection of molecular ions.

  6. Ion exhange and molecular sorption of oxalic acid with a highly basic anion exchanger

    NASA Astrophysics Data System (ADS)

    Krisilova, E. V.; Oros, G. Yu.; Krisilov, A. V.; Selemenev, V. F.

    2014-04-01

    Ab initio modeling of a matrix fragment of resin and geometry optimization of the molecular structure of oxalic acid were performed. The isotherm of oxalic acid sorption with AV-17-8 anion exchange resin was obtained by the variable concentrations technique. The ion-exchange and molecular components of sorbate fixation with the ion exchanger were determined. The hydration of the highly basic anion exchanger that absorbed different quantities of dicarboxylic acid was evaluated by the centrifuging method. The dependence of the amount of water and sorbate concentration in the resin was linear antibatic.

  7. Improvement of Contact Resistance with Molecular Ion Implantation

    SciTech Connect

    Lee, Kyung Won; Lee, Jin Ku; Oh, Jae Geun; Ju, Min Ae; Jeon, Seung Joon; Ku, Ja Chun; Park, Sung Ki; Huh, Tae Hoon; Kim, Steve; Ra, Geum Joo; Harris, Mark A.; Reece, Ronald N.; Yoon, Dae Ho

    2008-11-03

    Basic characteristics of ClusterBoron (B{sub 18}H{sub 22}) implantation were investigated for improving contact resistance in DRAM devices. Generally, {sup 49}BF{sub 2} has been widely used for contact implant application in DRAM manufacturing because of its higher productivity compared to monomer boron ({sup 11}B). However, because of limited activation in a low thermal budget ({approx}800 deg. C) anneal, the sheet resistance was saturated for doses over 5x10{sup 15} ions/cm{sup 2}. Although many investigations have been reported, such as {sup 30}BF implant mixed implant with monomer boron etc., no practical solution has been found for dramatic improvement of contact resistance in a productive manner. B{sub 18}H{sub 22} was developed to overcome the productivity limitations encountered in low energy, high dose boron implantation and the limited activation of {sup 49}BF{sub 2} due to co-implanted fluorine. In this study, basic characterization of the B{sub 18}H{sub 22} contact implant was performed through sheet resistance, SIMS (Secondary Ion Mass Spectrometry) and XTEM (cross-sectional transmission electron microscopy). The B{sub 18}H{sub 22} implants showed lower sheet resistance than conventional {sup 49}BF{sub 2} for 5x10{sup 15} ions/cm{sup 2} on bare wafer tests. Through XTEM study, we found the activation behavior of both B{sub 18}H{sub 22} and {sup 49}BF{sub 2} were directly related with the amorphous layer thickness and residual defects from low thermal budget anneal. PMOS contact resistance in the sub-70 nm device by B{sub 18}H{sub 22} implantation showed considerable improvement (about 30%), showing B{sub 18}H{sub 22} could replace the BF{sub 2} for contact implant in contact resistance implant.

  8. Toward Molecular 4f Single-Ion Magnet Qubits.

    PubMed

    Pedersen, Kasper S; Ariciu, Ana-Maria; McAdams, Simon; Weihe, Høgni; Bendix, Jesper; Tuna, Floriana; Piligkos, Stergios

    2016-05-11

    Quantum coherence is detected in the 4f single-ion magnet (SIM) Yb(trensal), by isotope selective pulsed EPR spectroscopy on an oriented single crystal. At X-band, the spin-lattice relaxation (T1) and phase memory (Tm) times are found to be independent of the nuclei bearing, or not, a nuclear spin. The observation of Rabi oscillations of the spin echo demonstrates the possibility to coherently manipulate the system for more than 70 rotations. This renders Yb(trensal), a sublimable and chemically modifiable SIM, an excellent candidate for quantum information processing. PMID:27105449

  9. Changes in the molecular ion yield and fragmentation of peptides under various primary ions in ToF-SIMS and matrix-enhanced ToF-SIMS.

    PubMed

    Körsgen, Martin; Tyler, Bonnie J; Pelster, Andreas; Lipinsky, Dieter; Dreisewerd, Klaus; Arlinghaus, Heinrich F

    2016-06-01

    Time of flight secondary ion mass spectrometry (ToF-SIMS) is a powerful technique for the nanoanalysis of biological samples, but improvements in sensitivity are needed in order to detect large biomolecules, such as peptides, on the individual cell level at physiological concentrations. Two promising options to improve the sensitivity of SIMS to large peptides are the use of cluster primary ions to increase desorption of intact molecules or the use of matrix-assisted laser desorption/ionization (MALDI) matrices to increase the ionization probability. In this paper, the authors have combined these two approaches in order to improve understanding of the interaction between ionization and fragmentation processes. The peptides bradykinin and melittin were prepared as neat monolayers on silicon, in a Dextran-40 matrix and in two common MALDI matrices, 2,5-dihydroxybenzoic acid (DHB) and α-cyano-4-hydroxy cinnamic acid (HCCA). ToF-SIMS spectra of these samples were collected using a range of small Bi cluster primary ions and large Ar cluster primary ions. The trends observed in the molecular ion yield and the [M+H](+)/C4H8N(+) ratio with primary ion cluster size were sample system dependent. The molecular ion yield of the bradykinin was maximized by using 30 keV Bi3 (+) primary ions in a DHB matrix but in the HCCA matrix, the maximum molecular ion yield was obtained by using 30 keV Bi7 (+) primary ions. In contrast, the molecular ion yield for melittin in both matrices was greatest using 20 keV Ar2000 (+) primary ions. Improvements in the molecular ion yield were only loosely correlated with a decrease in small fragment ions. The data indicate a complex interplay between desorption processes and ion formation processes which mean that the optimal analytical conditions depend on both the target analyte and the matrix. PMID:26829968

  10. Reversing Molecular Ion Formation for Quantum Simulations in a Coulomb Crystal of Be+ Ions

    NASA Astrophysics Data System (ADS)

    Sawyer, Brian; Bohnet, Justin; Britton, Joseph; Bollinger, John

    2015-05-01

    For more than a decade, the internal states of cold, trapped atomic ions have been used as qubits for quantum logic operations. Penning traps allow for confinement and manipulation of very large ion crystals (>> 100) in 1D, 2D, or 3D configurations. Quantum simulation experiments with 2D crystals in Penning traps rely on engineered couplings between Be+ internal spin and collective ion motion perpendicular to the crystal plane. High-fidelity quantum logic operations require precise knowledge of the crystal mode structure, but mode eigenfrequencies and eigenvectors can shift over time as impurity hydride ions (i.e. BeH+) are formed in the crystal via chemistry with background H2 molecules in the vacuum chamber. To mitigate this, we have demonstrated a single-photon photodissociation scheme for BeH+ that efficiently recovers Be+ ions within the crystal. A commercial excimer laser operating at 157 nm provides the photodissociation light, and we note that a 193 nm excimer should efficiently recover Mg+ and Al+ from their respective hydride species, making this technique applicable to a wide range of ion species used in quantum information experiments. Supported by a NIST-NRC Fellowship.

  11. Ion-beam assisted deposition of thin molybdenum films studied by molecular dynamics simulation

    NASA Astrophysics Data System (ADS)

    Robbemond, Arie; Thijsse, Barend J.

    1997-05-01

    We report results obtained by molecular dynamics simulation of low energy argon-ion assisted growth of thin molybdenum films (≈ 20 Å). The effects of a single ion impact are discussed, but more particularly we consider film growth from a manufacturing viewpoint and examine the properties of the completed films. Results for ion-beam assisted deposition are compared with those for unassisted growth (i.e. physical vapor deposition). Surface orientation, atomic displacements, surface roughness, sputtering, point defects, and the influence of off-normal atom incidence are discussed.

  12. When electrons meet molecular ions and what happens next: dissociative recombination from interstellar molecular clouds to internal combustion engines.

    PubMed

    Thomas, Richard D

    2008-01-01

    The interaction of matter with its environment is the driving force behind the evolution of 99% of the observed matter in the universe. The majority of the visible universe exists in a state of weak ionization, the so called fourth state of matter: plasma. Plasmas are ubiquitous, from those occurring naturally; interstellar molecular clouds, cometary comae, circumstellar shells, to those which are anthropic in origin; flames, combustion engines and fusion reactors. The evolution of these plasmas is driven by the interaction of the plasma constituents, the ions, and the electrons. One of the most important subsets of these reactions is electron-molecular ion recombination. This process is significant for two very important reasons. It is an ionization reducing reaction, removing two ionised species and producing neutral products. Furthermore, these products may themselves be reactive radical species which can then further drive the evolution of the plasma. The rate at which the electron reacts with the ion depends on many parameters, for examples the collision energy, the internal energy of the ion, and the structure of the ion itself. Measuring these properties together with the manner in which the system breaks up is therefore critical if the evolution of the environment is to be understood at all. Several techniques have been developed to study just such reactions to obtain the necessary information on the parameters. In this paper the focus will be on one the most recently developed of these, the Ion Storage Ring, together with the detection tools and techniques used to extract the necessary information from the reaction. PMID:18618616

  13. Vibrational Spectroscopy of Sympathetically Cooled CaH^+ Molecular Ions

    NASA Astrophysics Data System (ADS)

    Khanyile, Ncamiso B.; Goeders, James E.; Brown, Kenneth R.

    2013-06-01

    The search for time variation in the fundamental constants of nature such as the fine structure constant(α) and the proton/electron mass ratio(μ), is an area of active research. Comparing the vibrational overtones of CaH^+ with electronic transitions in atoms has been proposed as a means to detect possible time variation of μ Before these precision measurements can be realized, the survey spectroscopy needs to be performed. We describe our experiments using a Coulomb crystal of sympathetically cooled CaH^+ and laser-cooled Ca^+ ions to measure the vibrational overtones by resonance-enhanced multiphoton photo-dissociation (REMPD) in a linear Paul trap. The dissociation of CaH^+ is detected by observing the change in the crystal composition by monitoring the Ca^+ fluorescence. Future single ion experiments for the precision measurement are also discussed. J. Uzan, Rev. Mod. Phys. 75, 403 (2003). M. Kajita and Y. Moriwaki, J. Phys. B: At. Mol. Opt. Phys. 42, 154022(2009).

  14. Rotational dynamics of a diatomic molecular ion in a Paul trap

    SciTech Connect

    Hashemloo, A.; Dion, C. M.

    2015-11-28

    We present models for a heteronuclear diatomic molecular ion in a linear Paul trap in a rigid-rotor approximation, one purely classical and the other where the center-of-mass motion is treated classically, while rotational motion is quantized. We study the rotational dynamics and their influence on the motion of the center-of-mass, in the presence of the coupling between the permanent dipole moment of the ion and the trapping electric field. We show that the presence of the permanent dipole moment affects the trajectory of the ion and that it departs from the Mathieu equation solution found for atomic ions. For the case of quantum rotations, we also evidence the effect of the above-mentioned coupling on the rotational states of the ion.

  15. Rotational dynamics of a diatomic molecular ion in a Paul trap.

    PubMed

    Hashemloo, A; Dion, C M

    2015-11-28

    We present models for a heteronuclear diatomic molecular ion in a linear Paul trap in a rigid-rotor approximation, one purely classical and the other where the center-of-mass motion is treated classically, while rotational motion is quantized. We study the rotational dynamics and their influence on the motion of the center-of-mass, in the presence of the coupling between the permanent dipole moment of the ion and the trapping electric field. We show that the presence of the permanent dipole moment affects the trajectory of the ion and that it departs from the Mathieu equation solution found for atomic ions. For the case of quantum rotations, we also evidence the effect of the above-mentioned coupling on the rotational states of the ion. PMID:26627960

  16. Ion Transport through Membrane-Spanning Nanopores Studied by Molecular Dynamics Simulations and Continuum Electrostatics Calculations

    PubMed Central

    Peter, Christine; Hummer, Gerhard

    2005-01-01

    Narrow hydrophobic regions are a common feature of biological channels, with possible roles in ion-channel gating. We study the principles that govern ion transport through narrow hydrophobic membrane pores by molecular dynamics simulation of model membranes formed of hexagonally packed carbon nanotubes. We focus on the factors that determine the energetics of ion translocation through such nonpolar nanopores and compare the resulting free-energy barriers for pores with different diameters corresponding to the gating regions in closed and open forms of potassium channels. Our model system also allows us to compare the results from molecular dynamics simulations directly to continuum electrostatics calculations. Both simulations and continuum calculations show that subnanometer wide pores pose a huge free-energy barrier for ions, but a small increase in the pore diameter to ∼1 nm nearly eliminates that barrier. We also find that in those wider channels the ion mobility is comparable to that in the bulk phase. By calculating local electrostatic potentials, we show that the long range Coulomb interactions of ions are strongly screened in the wide water-filled channels. Whereas continuum calculations capture the overall energetics reasonably well, the local water structure, which is not accounted for in this model, leads to interesting effects such as the preference of hydrated ions to move along the pore wall rather than through the center of the pore. PMID:16006629

  17. Building up water-wire clusters: isomer-selective ultraviolet and infrared spectra of jet-cooled 2-aminopurine (H2O)n, n = 2 and 3.

    PubMed

    Lobsiger, Simon; Sinha, Rajeev K; Leutwyler, Samuel

    2013-10-17

    2-Aminopurine (2AP) is an adenine analogue with a high fluorescence quantum yield in water solution, which renders it a useful real-time probe of DNA structure. We report the ultraviolet (UV) and infrared (IR) spectra of size-selected and jet-cooled 9H-2AP·(H2O)n clusters with n = 2 and 3. Mass- and species-specific UV/UV holeburning spectroscopy allows to separate the UV spectra of four cluster isomers in the 31,200–33,000 cm(–1) spectral region with electronic band origins at 31339, 31450, 31891, and 32163 cm(–1). Using IR/UV depletion spectroscopy in combination with B3LYP calculated harmonic vibrational frequencies, the H-bonding topologies of two isomers of the n = 2 and of two isomers of the n = 3 cluster are identified. One n = 2 isomer (denoted 2A) forms a water dimer chain between the N9H and N3 atoms at the sugar-edge site, the other isomer (denoted 2D) binds one H2O at the sugar-edge site and the other at the trans-amino site between the N1 atom and the NH2 group. For 2-aminopurine·(H2O)3, one isomer (denoted 3A) forms an H-bonded water wire at the sugar-edge site, while isomer 3B accommodates two H2O molecules at the sugar-edge and one at the trans-amino site. The approximate second-order coupled cluster (CC2) method predicts the adiabatic S1 ← S0 transitions of 9H-2-aminopurine and six water cluster isomers with n = 1–3 in very good agreement with the experimental 0(0)(0) frequencies, with differences of <0.6%. The stabilization of the S1(ππ*) state of 2-aminopurine by water clusters is highly regiospecific: Isomers with one or two H2O molecules H-bonded in the trans-amino position induce large spectra red shifts, corresponding to 1ππ* state stabilization of 10–12 kJ/mol, while water-wire cluster solvation at the sugar-edge leads to much smaller stabilization. The evolution of the IR spectra of the water-wire clusters with n = 1–3 that are H-bonded to the sugar-edge site is discussed. Qualitatively different regions (denoted I to IV

  18. High resolution spectroscopy of jet cooled phenyl radical: The ν1 and ν2 a1 symmetry C-H stretching modes

    NASA Astrophysics Data System (ADS)

    Chang, Chih-Hsuan; Nesbitt, David J.

    2016-07-01

    A series of CH stretch modes in phenyl radical (C6H5) has been investigated via high resolution infrared spectroscopy at sub-Doppler resolution (˜60 MHz) in a supersonic discharge slit jet expansion. Two fundamental vibrations of a1 symmetry, ν1 and ν2, are observed and rotationally analyzed for the first time, corresponding to in-phase and out-of-phase symmetric CH stretch excitation at the ortho/meta/para and ortho/para C atoms with respect to the radical center. The ν1 and ν2 band origins are determined to be 3073.968 50(8) cm-1 and 3062.264 80(7) cm-1, respectively, which both agree within 5 cm-1 with theoretical anharmonic scaling predictions based on density functional B3LYP/6-311g++(3df,3dp) calculations. Integrated band strengths for each of the CH stretch bands are analyzed, with the relative intensities agreeing remarkably well with theoretical predictions. Frequency comparison with previous low resolution Ar-matrix spectroscopy [A. V. Friderichsen et al., J. Am. Chem. Soc. 123, 1977 (2001)] reveals a nearly uniform Δν ≈ + 10-12 cm-1 blue shift between gas phase and Ar matrix values for ν1 and ν2. This differs substantially from the much smaller red shift (Δν ≈ - 1 cm-1) reported for the ν19 mode, and suggests a simple physical model in terms of vibrational mode symmetry and crowding due to the matrix environment. Finally, the infrared phenyl spectra are well described by a simple asymmetric rigid rotor Hamiltonian and show no evidence for spectral congestion due to intramolecular vibrational coupling, which bodes well for high resolution studies of other ring radicals and polycyclic aromatic hydrocarbons. In summary, the combination of slit jet discharge methods with high resolution infrared lasers enables spectroscopic investigation of even highly reactive combustion and interstellar radical intermediates under gas phase, jet-cooled (Trot ≈ 11 K) conditions.

  19. High resolution spectroscopy of jet cooled phenyl radical: The ν1 and ν2 a1 symmetry C-H stretching modes.

    PubMed

    Chang, Chih-Hsuan; Nesbitt, David J

    2016-07-28

    A series of CH stretch modes in phenyl radical (C6H5) has been investigated via high resolution infrared spectroscopy at sub-Doppler resolution (∼60 MHz) in a supersonic discharge slit jet expansion. Two fundamental vibrations of a1 symmetry, ν1 and ν2, are observed and rotationally analyzed for the first time, corresponding to in-phase and out-of-phase symmetric CH stretch excitation at the ortho/meta/para and ortho/para C atoms with respect to the radical center. The ν1 and ν2 band origins are determined to be 3073.968 50(8) cm(-1) and 3062.264 80(7) cm(-1), respectively, which both agree within 5 cm(-1) with theoretical anharmonic scaling predictions based on density functional B3LYP/6-311g++(3df,3dp) calculations. Integrated band strengths for each of the CH stretch bands are analyzed, with the relative intensities agreeing remarkably well with theoretical predictions. Frequency comparison with previous low resolution Ar-matrix spectroscopy [A. V. Friderichsen et al., J. Am. Chem. Soc. 123, 1977 (2001)] reveals a nearly uniform Δν ≈ + 10-12 cm(-1) blue shift between gas phase and Ar matrix values for ν1 and ν2. This differs substantially from the much smaller red shift (Δν ≈ - 1 cm(-1)) reported for the ν19 mode, and suggests a simple physical model in terms of vibrational mode symmetry and crowding due to the matrix environment. Finally, the infrared phenyl spectra are well described by a simple asymmetric rigid rotor Hamiltonian and show no evidence for spectral congestion due to intramolecular vibrational coupling, which bodes well for high resolution studies of other ring radicals and polycyclic aromatic hydrocarbons. In summary, the combination of slit jet discharge methods with high resolution infrared lasers enables spectroscopic investigation of even highly reactive combustion and interstellar radical intermediates under gas phase, jet-cooled (Trot ≈ 11 K) conditions. PMID:27475358

  20. Kinetic Stability of Non-IPR Fullerene Molecular Ions.

    PubMed

    Aihara, Jun-ichi; Nakagami, Yuto; Sekine, Rika

    2015-06-18

    Many fullerenes that violate the isolated pentagon rule (IPR) form stable metallofullerenes. In general, a fullerene cage is kinetically stabilized by acquiring a given number of electrons. Kinetic stability of negatively charged non-IPR fullerenes, including the recently isolated endohedral metallofullerene with a heptagonal face, was rationalized in terms of bond resonance energy (BRE). Interestingly, molecular anions of conventional fullerenes found in most isolated metallofullerenes are kinetically stable with large positive BREs for all CC bonds. As we pointed out in 1993, the IPR does not apply to charged fullerenes because π-bonds shared by two five-membered rings are aromatized to varying extents. PMID:26020361

  1. Molecular mobility, morphology, and ion conduction in ionomers for electroactive devices

    NASA Astrophysics Data System (ADS)

    Tudryn, Gregory J.

    aggregation process in Na ionomers as ionic dipoles thermally randomize and lower the measured dielectric constant of the medium, leading to further aggregation. We observe amplified microphase-separation through ionic groups preferentially solvated by PEO chains, as seen in block copolymers with added salt. Even at 25%PEO / 75%PTMO the ionomers have VFT temperature dependence of conducting ion mobility, meaning that the 25% PEO/ion microphase is still continuous A model is developed to describe the frequency dependent storage and loss modulus and the delay in Rouse motion due to ion association lifetime, as functions of ion content and molecular weight for our low molecular weight ionomers. The ion rearrangement relaxation in dielectric spectroscopy is clearly the ion association lifetime that controls terminal dynamics in linear viscoelasticity, allowing a simple sticky Rouse model, using the most-probable distribution based on NMR Mn, to fully describe master curves of the frequency dependent storage and loss modulus. Using insight from ionic interaction strength, ionic liquids are used as counterions, effectively plasticizing the ionomers without added solvent. Ionic interactions were weakened with increasing counterion size, and with modification of cations using ether-oxygen, promoting self-solvation, which increases conducting ion density by an order of magnitude. Room temperature ionic liquids were subsequently used in combination with NafionRTM membranes as electroactive substrates to correlate ion transport to morphology as a function of volume fraction of ionic liquid. This study illuminated the critical volume uptake of ionic liquid in Nafion, identifying percolation of ionic pathways and a significant increase in dielectric constant at low frequencies, indicating an increase in the number density of ions capable of polarizing at the electrode surface. Consequently, the fundamental information obtained about the structure-property relations of ionomers can be used

  2. Photochemistry and molecular ions in carbon-rich circumstellar envelopes

    NASA Technical Reports Server (NTRS)

    Glassgold, A. E.; Mamon, G. A.; Omont, A.; Lucas, R.

    1987-01-01

    An earlier theory of ionization of C-rich circumstellar envelopes based on the photochemical model is extended to include the temperature dependence of ion-molecule reactions with polar molecules, particularly HCN, and line self-shielding of CO dissociating radiation. The results are applied to the abundances of HCO(+) and HNC in C-rich circumstellar envelopes. With standard parameters for IRC + 10216, the model is found to be consistent with the new upper limit to the antenna temperature of the J = 1-0 line of HCO(+) obtained with the IRAM 30-m telescope. The photochemical model provides a natural explanation of the relatively large ratio of HCN to HNC observed for C-rich circumstellar envelopes, and good agreement is obtained for the H(C-13)N/HNC antenna temperature ratio measured for IRC + 10216.

  3. Lifetimes and stabilities of familiar explosives molecular adduct complexes during ion mobility measurements

    PubMed Central

    McKenzie, Alan; DeBord, John Daniel; Ridgeway, Mark; Park, Melvin; Eiceman, Gary; Fernandez-Lima, Francisco

    2015-01-01

    Trapped ion mobility spectrometry coupled to mass spectrometry (TIMS-MS) was utilized for the separation and identification of familiar explosives in complex mixtures. For the first time, molecular adduct complex lifetimes, relative stability, binding energies and candidate structures are reported for familiar explosives. Experimental and theoretical results showed that the adduct size and reactivity, complex binding energy and the explosive structure tailors the stability of the molecular adduct complex. TIMS flexibility to adapt the mobility separation as a function of the molecular adduct complex stability (i.e., short or long IMS experiments / low or high IMS resolution) permits targeted measurements of explosives in complex mixtures with higher confidence levels. PMID:26153567

  4. Indirect Terahertz Spectroscopy of Molecular Ions Using Highly Accurate and Precise Mid-Ir Spectroscopy

    NASA Astrophysics Data System (ADS)

    Mills, Andrew A.; Ford, Kyle B.; Kreckel, Holger; Perera, Manori; Crabtree, Kyle N.; McCall, Benjamin J.

    2009-06-01

    With the advent of Herschel and SOFIA, laboratory methods capable of providing molecular rest frequencies in the terahertz and sub-millimeter regime are increasingly important. As of yet, it has been difficult to perform spectroscopy in this wavelength region due to the limited availability of radiation sources, optics, and detectors. Our goal is to provide accurate THz rest frequencies for molecular ions by combining previously recorded microwave transitions with combination differences obtained from high precision mid-IR spectroscopy. We are constructing a Sensitive Resolved Ion Beam Spectroscopy setup which will harness the benefits of kinematic compression in a molecular ion beam to enable very high resolution spectroscopy. This ion beam is interrogated by continuous-wave cavity ringdown spectroscopy using a home-made widely tunable difference frequency laser that utilizes two near-IR lasers and a periodically-poled lithium niobate crystal. Here, we report our efforts to optimize our ion beam spectrometer and to perform high-precision and high-accuracy frequency measurements using an optical frequency comb. footnote

  5. Resonance-Raman-scattering spectroscopy for the halogen-molecular-ion centers in alkali halides

    NASA Astrophysics Data System (ADS)

    Suzuki, T.; Tanimura, K.; Itoh, N.

    1993-10-01

    We have measured the Raman scattering in resonance with the bonding-to-antibonding transitions of two types of dihalogen-molecular-ion centers in alkali halides, the VK and H centers; the molecular ion occupies two adjacent halogen sites in the former and a single halogen site in the latter. It is found that the stretching-vibration frequency of the molecular ion is higher by more than 30% for the H center than for the VK center. The hardening is ascribed to the bond tightening due to the Madelung potential. Although the Raman line due to the stretching vibration consists of a single line in most alkali halides, two closely lying lines are observed for the H centers in alkali halides with small alkali-metal to halogen radius ratio and also for the VK center in NaCl. The paired-line structure is ascribed to the coupling of the stretching vibration of the halogen molecular ion with the lattice.

  6. Rotational energy of the hydrogen molecular ion in a magnetic field

    SciTech Connect

    Maluendes, S.A.; Fernandez, F.M.; Castro, E.A.

    1983-10-01

    A general method which combines hypervirial relations with the Hellmann-Feynman theorem and perturbation theory is applied in order to calculate the rotational eigenvalues of the hydrogen molecular ion in a magnetic field. Analytical expressions as well as numerical results are presented for both low and high field strengths.

  7. Modeling of ion complexation and extraction using substructural molecular fragments

    PubMed

    Solov'ev; Varnek; Wipff

    2000-05-01

    A substructural molecular fragment (SMF) method has been developed to model the relationships between the structure of organic molecules and their thermodynamic parameters of complexation or extraction. The method is based on the splitting of a molecule into fragments, and on calculations of their contributions to a given property. It uses two types of fragments: atom/bond sequences and "augmented atoms" (atoms with their nearest neighbors). The SMF approach is tested on physical properties of C2-C9 alkanes (boiling point, molar volume, molar refraction, heat of vaporization, surface tension, melting point, critical temperature, and critical pressures) and on octanol/water partition coefficients. Then, it is applied to the assessment of (i) complexation stability constants of alkali cations with crown ethers and phosphoryl-containing podands, and of beta-cyclodextrins with mono- and 1,4-disubstituted benzenes, and (ii) solvent extraction constants for the complexes of uranyl cation by phosphoryl-containing ligands. PMID:10850791

  8. Rotationsal and vibrational spectra of molecular ions: Feasibility of laboratory and astrophysical observation

    NASA Technical Reports Server (NTRS)

    Woods, R. C.; Certain, P. R.; Bernstein, R. B.

    1974-01-01

    The rotational spectra of a number of small molecular ions should be detectable in the microwave or millimeter wave regions in laboratory experiments using currently available techniques. The dipole moments and absorption coefficients of polar diatomics CO(+) and NO(+) as well as asymmetric isotopically enriched species, like O-18O-16(+), NE-20NE-22(+), and OC-18 O-16(+) are calculated to be sufficiently large to allow observation of their spectra. In addition to the detailed molecular structure information which such spectral data would provide, precise knowledge of the transition frequencies would render likely the detection of certain of these ions in the interstellar sources or in planetary atmospheres. All of these ions also possess vibrational spectra which should be detectable in the infrared region in laboratory or astrophysical sources.

  9. Dysregulation of transition metal ion homeostasis is the molecular basis for cadmium toxicity in Streptococcus pneumoniae

    PubMed Central

    Begg, Stephanie L.; Eijkelkamp, Bart A.; Luo, Zhenyao; Couñago, Rafael M.; Morey, Jacqueline R.; Maher, Megan J.; Ong, Cheryl-lynn Y.; McEwan, Alastair G.; Kobe, Bostjan; O’Mara, Megan L.; Paton, James C.; McDevitt, Christopher A.

    2015-01-01

    Cadmium is a transition metal ion that is highly toxic in biological systems. Although relatively rare in the Earth’s crust, anthropogenic release of cadmium since industrialization has increased biogeochemical cycling and the abundance of the ion in the biosphere. Despite this, the molecular basis of its toxicity remains unclear. Here we combine metal-accumulation assays, high-resolution structural data and biochemical analyses to show that cadmium toxicity, in Streptococcus pneumoniae, occurs via perturbation of first row transition metal ion homeostasis. We show that cadmium uptake reduces the millimolar cellular accumulation of manganese and zinc, and thereby increases sensitivity to oxidative stress. Despite this, high cellular concentrations of cadmium (~17 mM) are tolerated, with negligible impact on growth or sensitivity to oxidative stress, when manganese and glutathione are abundant. Collectively, this work provides insight into the molecular basis of cadmium toxicity in prokaryotes, and the connection between cadmium accumulation and oxidative stress. PMID:25731976

  10. Systematics in a measurement of the electron's electric dipole moment using trapped molecular ions

    NASA Astrophysics Data System (ADS)

    Grau, Matt; Cossel, Kevin; Cairncross, William; Gresh, Dan; Zhou, Yan; Ye, Jun; Cornell, Eric

    2015-05-01

    A precision measurement of the electron's electric dipole moment (EDM) has important implications for physics beyond the Standard Model. Trapped molecular ions offer high sensitivity in such an experiment because of the large effective electric fields and long coherence times that are possible. Our experiment uses Ramsey spectroscopy of HfF+ ions in a linear RF trap with rotating bias fields, achieving coherence times beyond 1 second for 1000 trapped ions. Compared to other electron EDM experiments that use molecular beams, we will be sensitive to a different class of systematic errors. In this work we investigate systematic errors arising from all fields involved in the experiment, including the trapping and polarizing electric fields, magnetic field gradients, and motional effects such as geometric phases. This work was supported by NIST and NSF.

  11. Properties of solvate shells and the mobility of ions, according to molecular dynamics data

    NASA Astrophysics Data System (ADS)

    Lankin, A. V.; Norman, G. E.; Orekhov, M. A.

    2016-05-01

    The solvate shells of an ion, its velocity autocorrelation function, and diffusion coefficient D are found, and the interrelations between them are analyzed. A single ion in the system of atoms of a liquid is considered a model system. The interaction between the ion and atoms of the liquid is described by polarization potential U( r); the interaction between atoms of the liquid alone is described by the Lennard-Jones potential. A classical molecular dynamics method is used. Five solvate shells around the ion are found, and the lifetimes of atoms on each shell are calculated. It is found that the velocity autocorrelation function is of a vibrating nature. The spectrum of the autocorrelator and the frequency of cluster vibrations in a linear approximation are compared. Dependences D on parameters of potential U( r) are found. No dependence D on the ion mass is found; this is explained by solvation. The Einstein-Stokes formula and the HSK approximation are used in discussing the results. It is shown that at small radii of the ion, dependence D on parameters U( r) is described by such a model. When the ion radius is increased, the deviation from this dependence and an increase in D are observed. The results are compared to experimental mobilities of O 2 - and Ar 2 + ions in liquid argon.

  12. Microwave Spectrum of the SD+3 Ion: Molecular Structure.

    PubMed

    Araki; Ozeki; Saito

    1998-11-01

    The J = 1-0 to 4-3 spectral lines of SD+3 were measured in the 152-610 GHz region using a source-modulated microwave spectrometer. The SD+3 ion was generated in a free space absorption cell by a hollow-cathode discharge in a gas mixture of D2S and D2. The rotational constant B0 and the centrifugal distortion constants DJ and DJK were determined from the measured frequencies. A vibration-rotation analysis was carried out and the rz structures of SH+3 and SD+3 were derived from their zero point averaged rotational constants, expressed as SH+3: rz = 1.36512(22) Å and thetaz = 94.098(26) degrees, and SD+3: rz = 1.36086(16) Å and thetaz = 94.1211(195) degrees, where the difference between thetaz(HSH) and thetaz(DSD) was assumed to be the same as that between thetaz(HPH) of PH3 and thetaz(DPD) of PD3. From the shift between the rz structures of SH+3 and SD+3, the re structure of SH+3 was estimated to be re = 1.35001(113) Å, thetae = 94.181(135) degrees. Copyright 1998 Academic Press. PMID:9770407

  13. Theoretical study of swift molecular ions specularly reflected from solid surfaces under glancing angle of incidence

    NASA Astrophysics Data System (ADS)

    Song, Yuan-Hong; Wang, You-Nian; Mišković, Z. L.

    2005-04-01

    We develop a theoretical model to study grazing scattering of fast diatomic molecular ions from a solid surface, based on the dielectric response formalism within the specular reflection model, where the plasmon pole approximation for dielectric function is employed to describe the single-particle and the collective excitations of the electron gas at the surface. Evolution of the bound-electron densities at the constituent ions of a molecule in the course of scattering is described by an approach similar to recent implementation of the Brandt-Kitagawa model for single-ion surface grazing scattering. We solve numerically the equations of motion for the constituent ions and obtain the ion scattering trajectories in the presence of Coulomb explosion modified by the surface wake potential, for the initial molecular-axis orientations in either random directions or along the beam. Vicinage effect on the total energy loss is discussed on the basis of analyzing the position-dependent stopping powers of individual ions and the interferences in the electron excitations of the substrate.

  14. A Investigation of a Possible Molecular Effect in Ion Atom Collision Using a Gaseous Argon Target

    NASA Astrophysics Data System (ADS)

    Arora, Sanjeev

    1992-01-01

    The present work deals with an investigation of the molecular effect, which is defined as the difference in experimental results using isotachic atomic ion and molecular ion beams in ion atom collisions. Previous studies have dealt almost exclusively with total cross section measurements. This thesis explores the idea that the molecular effect may be more pronounced in the differential ionization probability of the target atoms. Also, a gaseous argon target of sufficiently low density was used in order to ensure that the two correlated protons in the H _2^{+} beam did not interact with two adjacent target atoms simultaneously. We report that, contrary to the expectations noted above, the molecular effect in the K shell differential ionization probability of argon for scattering angles up to 90^circ appears to be no more than the molecular effect in the total ionization probability. The uncertainity in our results is statistical in nature and can be improved upon by running the experiment for a longer duration of time.

  15. Angle-resolved intensity and energy distributions of positive and negative hydrogen ions released from tungsten surface by molecular hydrogen ion impact

    NASA Astrophysics Data System (ADS)

    Kato, S.; Tanaka, N.; Sasao, M.; Kisaki, M.; Tsumori, K.; Nishiura, M.; Matsumoto, Y.; Kenmotsu, T.; Wada, M.; Yamaoka, H.

    2015-08-01

    Hydrogen ion reflection properties have been investigated following the injection of H+, H2+ and H3+ ions onto a polycrystalline W surface. Angle- and energy-resolved intensity distributions of both scattered H+ and H- ions are measured by a magnetic momentum analyzer. We have detected atomic hydrogen ions reflected from the surface, while molecular hydrogen ions are unobserved within our detection limit. The reflected hydrogen ion energy is approximately less than one-third of the incident beam energy for H3+ ion injection and less than a half of that for H2+ ion injection. Other reflection properties are very similar to those of monoatomic H+ ion injection. Experimental results are compared to the classical trajectory simulations using the ACAT code based on the binary collision approximation.

  16. Heavy ion induced mutations in mammalian cells: Cross sections and molecular analysis

    NASA Technical Reports Server (NTRS)

    Stoll, U.; Schmidt, P.; Schneider, E.; Kiefer, J.

    1994-01-01

    Our investigations of heavy ion-induced mutations in mammalian cells, which had been begun a few years ago, were systematically continued. For the first time, it was possible to cover a large LET range with a few kinds of ions. To do this, both UNILAC and SIS were used to yield comparable data for a large energy range. This is a necessary condition for a comprehensive description of the influence of such ion parameters as energy and LET. In these experiments, the induced resistance against the poison 6-thioguanin (6-TG), which is linked to the HPRT locus on the genome, is being used as mutation system. In addition to the mutation-induction cross-section measurements, the molecular changes of the DNA are being investigated by means of Multiplex PCR ('Polymerase Chain Reaction') gene amplification. From these experiments we expect further elucidation of the mutation-inducing mechanisms composing the biological action of heavy-ion radiation.

  17. Development of a Submillimeter Multipass Spectrometer for the Study of Molecular Ions

    NASA Astrophysics Data System (ADS)

    Carroll, A.; Rocher, B.; Laas, J. C.; Deprince, B. A.; Hays, B.; Weaver, S. L. Widicus; Lang, S.

    2012-06-01

    We have developed a multipass spectrometer for the submillimeter spectral region that is being used to study molecular ions through gas phase spectroscopy. The optical configuration is based on the design of Perry and coworkers that was implemented in the optical regime. To our knowledge, this is the first implementation of this optical configuration at long wavelengths. The setup involves two nearly concentric spherical mirrors that focus the multiple beam passes into a small area, or ``waist'', in the middle of the sample chamber. A supersonic molecular beam is coupled to the setup so that the molecular beam crosses the optical path at the waist. Initial studies have focused on neutral test molecules to probe the physical properties of the molecular beam under various arrangements of the molecular source relative to the optical path. Current studies focus on coupling a plasma discharge source to the setup to enable the study of molecular ions. Here we present the design of this instrument, compare the spectrometer capabilities to a traditional single pass spectrometer, and discuss the results of initial spectroscopic studies.

  18. Effect of Zn(2+) ions on the assembly of amylin oligomers: insight into the molecular mechanisms.

    PubMed

    Wineman-Fisher, Vered; Miller, Yifat

    2016-08-01

    Amylin is an endocrine hormone and is a member of the family of amyloid peptides and proteins that emerge as potential scaffolds by self-assembly processes. Zn(2+) ions can bind to amylin peptides to form self-assembled Zn(2+)-amylin oligomers. In the current work the binding sites of Zn(2+) ions in the self-assembled amylin oligomers at various concentrations of zinc have been investigated. Our results yield two conclusions. First, in the absence of Zn(2+) ions polymorphic states (i.e. various classes of amylin oligomers) are obtained, but when Zn(2+) ions bind to amylin peptides to form Zn(2+)-amylin oligomers, the polymorphism is decreased, i.e. Zn(2+) ions bind only to specific classes of amylin. At low concentrations of Zn(2+) ions the polymorphism is smaller than at high concentrations. Second, the structural features of the self-assembled amylin oligomers are not affected by the presence of Zn(2+) ions. This study proposes new molecular mechanisms of the self-assembly of Zn(2+)-amylin oligomers. PMID:27425207

  19. Calculations of fast ion collisions with multi-center molecular targets

    NASA Astrophysics Data System (ADS)

    Kirchner, Tom

    2011-05-01

    The theoretical treatment of ion-molecule collisions is challenging for several reasons: the systems have many degrees of freedom, a rather complex geometry, and the electron dynamics might be nonperturbative and involve electron-electron interaction effects. However, the interest in accurate calculations has been growing recently. An important reason for this development is the relevance of ion-molecule collisions for a number of fields, such as atmospheric science, and the understanding of radiation damage of biological tissue. We have developed a new approach to meet these challenges. It disregards rovibrational motion, but it does address the multi-center geometry of the system and the generally nonperturbative nature of the electron dynamics. The key ingredients are an expansion of the initially populated molecular orbitals in terms of a single-center basis and a spectral representation of the molecular Hamiltonian. This facilitates a separation of molecular geometry and collision dynamics and makes it possible to use well-established ion-atom methods with relatively minor modifications. We have extended our basis generator method to deal with the collision dynamics and report on results for ionization and fragmentation of water molecules by proton and He+ ion impact over wide ranges of collision energies. For the case of He+ impact this will include a discussion of effects due to the presence of the projectile electron. This work has been supported by the Natural Sciences and Engineering Research Council of Canada.

  20. Fourier transform spectroscopy of the Swan (d(sup 3)pi(sub g) - a(sup 3)pi(sub u)) system of the jet-cooled C2 molecule

    NASA Technical Reports Server (NTRS)

    Prasad, C. V. V.; Bernath, P. F.

    1994-01-01

    The Swan (d(sup 3)pi(sub g) - a(sup 3)pi(sub u)) system of the C2 molecule was produced in a jet-cooled corona excited supersonic expansion of helium using diazoacetonitrile as a percursor molecule. This spectrum was recorded using the McMath Fourier transform spectrometer of the National Solar Observatory at Kitt Peak. A total of nine bands with v prime = 0 to 3 and v prime prime = 0 to 4 in the range 16,570-22,760/cm were observed and rotationally analyzed. The C2 molecules in this source had a rotational temperature of only 90 K so that only the low-J lines were present in the spectrum. In some sense the low temperatures in the jet source simulate conditions in the interstellar medium. The Swan system of C2 was also produced in a composite wall hollow cathode made Al4C3/Cu, and the rotational structure of the 1-0, 2-1, 3-2, 0-0, and 1-1 bands were analyzed. The data obtained from both these spectra were fitted together along with some recently published line positions. The rotational constants, lambda doubling parameters and the vibrational constants were estimated from this global fit. Our work on jet-cooled C2 follows similar work on the violet and red systems of CN. A summary of this CN work is also presented. also presented.

  1. Ion-water and ion-polypeptide correlations in a gramicidin-like channel. A molecular dynamics study.

    PubMed Central

    Jordan, P C

    1990-01-01

    This work describes a molecular dynamics study of ion-water and ion-polypeptide correlation in a model gramicidin-like channel (the polyglycine analogue) based upon interaction between polarizable, multipolar groups. The model suggests that the vicinity of the dimer junction and of the ethanolamine tail are regions of unusual flexibility. Cs+ binds weakly in the mouth of the channel: there it coordinates five water molecules and the #11CO group with which it interacts strongly and is ideally aligned. In the channel interior it is generally pentacoordinate; at the dimer junction, because of increased channel flexibility, it again becomes essentially hexacoordinate. The ion is also strongly coupled to the #13 CO but not to either #9 or #15, consistent with 13C NMR data. Water in the channel interior is strikingly different from bulk water; it has a much lower mean dipole moment. This correlates with our observation (which differs from that of previous studies) that water-water angular correlations do not persist within the channel, a result independent of ion occupancy or ionic polarity. In agreement with streaming potential measurements, there are seven single file water molecules associated with Cs+ permeation; one of these is always in direct contact with bulk water. At the mouth of an ion-free channel, there is a pattern of dipole moment alteration among the polar groups. Due to differential interaction with water, exo-carbonyls have unusually large dipole moments whereas those of the endo-carbonyls are low. The computed potential of mean force for CS+ translocation is qualitatively reasonable. However, it only exhibits a weakly articulated binding site and it does not quantitatively account for channel energetics. Correction for membrane polarization reduces, but does not eliminate, these problems. PMID:1705448

  2. A molecular-gap device for specific determination of mercury ions

    NASA Astrophysics Data System (ADS)

    Guo, Zheng; Liu, Zhong-Gang; Yao, Xian-Zhi; Zhang, Kai-Sheng; Chen, Xing; Liu, Jin-Huai; Huang, Xing-Jiu

    2013-11-01

    Specific determination/monitoring of trace mercury ions (Hg2+) in environmental water is of significant importance for drinking safety. Complementarily to conventional inductively coupled plasma mass spectrometry and atomic emission/absorption spectroscopy, several methods, i.e., electrochemical, fluorescent, colorimetric, and surface enhanced Raman scattering approaches, have been developed recently. Despite great success, many inevitably encounter the interferences from other metal ions besides the complicated procedures and sophisticated equipments. Here we present a molecular-gap device for specific determination of trace Hg2+ in both standardized solutions and environmental samples based on conductivity-modulated glutathione dimer. Through a self-assembling technique, a thin film of glutathione monolayer capped Au nanoparticles is introduced into 2.5 μm-gap-electrodes, forming numerous double molecular layer gaps. Notably, the fabricated molecular-gap device shows a specific response toward Hg2+ with a low detection limit actually measured down to 1 nM. Theoretical calculations demonstrate that the specific sensing mechanism greatly depends on the electron transport ability of glutathione dimer bridged by heavy metal ions, which is determined by its frontier molecular orbital, not the binding energy.

  3. Linking molecular models with ion mobility experiments. Illustration with a rigid nucleic acid structure

    PubMed Central

    D'Atri, Valentina; Porrini, Massimiliano; Rosu, Frédéric; Gabelica, Valérie

    2015-01-01

    Ion mobility spectrometry experiments allow the mass spectrometrist to determine an ion's rotationally averaged collision cross section ΩEXP. Molecular modelling is used to visualize what ion three-dimensional structure(s) is(are) compatible with the experiment. The collision cross sections of candidate molecular models have to be calculated, and the resulting ΩCALC are compared with the experimental data. Researchers who want to apply this strategy to a new type of molecule face many questions: (1) What experimental error is associated with ΩEXP determination, and how to estimate it (in particular when using a calibration for traveling wave ion guides)? (2) How to generate plausible 3D models in the gas phase? (3) Different collision cross section calculation models exist, which have been developed for other analytes than mine. Which one(s) can I apply to my systems? To apply ion mobility spectrometry to nucleic acid structural characterization, we explored each of these questions using a rigid structure which we know is preserved in the gas phase: the tetramolecular G-quadruplex [dTGGGGT]4, and we will present these detailed investigation in this tutorial. © 2015 The Authors. Journal of Mass Spectrometry published by John Wiley & Sons Ltd. PMID:26259654

  4. Molecularly imprinted porous beads for the selective removal of copper ions.

    PubMed

    Younis, M Rizwan; Bajwa, Sadia Z; Lieberzeit, Peter A; Khan, Waheed S; Mujahid, Adnan; Ihsan, Ayesha; Rehman, Asma

    2016-02-01

    In the present work, novel molecularly imprinted polymer porous beads for the selective separation of copper ions have been synthesized by combining two material-structuring techniques, namely, molecular imprinting and oil-in-water-in-oil emulsion polymerization. This method produces monodisperse spherical beads with an average diameter of ∼2-3 mm, in contrast to adsorbents produced in the traditional way of grinding and sieving. Field-emission scanning electron microscopy indicates that the beads are porous in nature with interconnected pores of about 25-50 μm. Brunner-Emmett-Teller analysis shows that the ion-imprinted beads possess a high surface area (8.05 m(2) /g), and the total pore volume is determined to be 0.00823 cm(3) /g. As a result of the highly porous nature and ion-imprinting, the beads exhibit a superior adsorption capacity (84 mg/g) towards copper than the non-imprinted material (22 mg/g). Furthermore, selectivity studies indicate that imprinted beads show splendid recognizing ability, that is, nearly fourfold greater selective binding for Cu(2+) in comparison to the other bivalent ions such as Mn(2+) , Ni(2+) , Co(2+) , and Ca(2+) . The imprinted composite beads prepared in this study possess uniform porous morphology and may open up new possibilities for the selective removal of copper ions from waste water/contaminated matrices. PMID:26632078

  5. Combining molecular dynamics and an electrodiffusion model to calculate ion channel conductance

    NASA Astrophysics Data System (ADS)

    Wilson, Michael A.; Nguyen, Thuy Hien; Pohorille, Andrew

    2014-12-01

    Establishing the relation between the structures and functions of protein ion channels, which are protein assemblies that facilitate transmembrane ion transport through water-filled pores, is at the forefront of biological and medical sciences. A reliable way to determine whether our understanding of this relation is satisfactory is to reproduce the measured ionic conductance over a broad range of applied voltages. This can be done in molecular dynamics simulations by way of applying an external electric field to the system and counting the number of ions that traverse the channel per unit time. Since this approach is computationally very expensive we develop a markedly more efficient alternative in which molecular dynamics is combined with an electrodiffusion equation. This alternative approach applies if steady-state ion transport through channels can be described with sufficient accuracy by the one-dimensional diffusion equation in the potential given by the free energy profile and applied voltage. The theory refers only to line densities of ions in the channel and, therefore, avoids ambiguities related to determining the surface area of the channel near its endpoints or other procedures connecting the line and bulk ion densities. We apply the theory to a simple, model system based on the trichotoxin channel. We test the assumptions of the electrodiffusion equation, and determine the precision and consistency of the calculated conductance. We demonstrate that it is possible to calculate current/voltage dependence and accurately reconstruct the underlying (equilibrium) free energy profile, all from molecular dynamics simulations at a single voltage. The approach developed here applies to other channels that satisfy the conditions of the electrodiffusion equation.

  6. Combining molecular dynamics and an electrodiffusion model to calculate ion channel conductance.

    PubMed

    Wilson, Michael A; Nguyen, Thuy Hien; Pohorille, Andrew

    2014-12-14

    Establishing the relation between the structures and functions of protein ion channels, which are protein assemblies that facilitate transmembrane ion transport through water-filled pores, is at the forefront of biological and medical sciences. A reliable way to determine whether our understanding of this relation is satisfactory is to reproduce the measured ionic conductance over a broad range of applied voltages. This can be done in molecular dynamics simulations by way of applying an external electric field to the system and counting the number of ions that traverse the channel per unit time. Since this approach is computationally very expensive we develop a markedly more efficient alternative in which molecular dynamics is combined with an electrodiffusion equation. This alternative approach applies if steady-state ion transport through channels can be described with sufficient accuracy by the one-dimensional diffusion equation in the potential given by the free energy profile and applied voltage. The theory refers only to line densities of ions in the channel and, therefore, avoids ambiguities related to determining the surface area of the channel near its endpoints or other procedures connecting the line and bulk ion densities. We apply the theory to a simple, model system based on the trichotoxin channel. We test the assumptions of the electrodiffusion equation, and determine the precision and consistency of the calculated conductance. We demonstrate that it is possible to calculate current/voltage dependence and accurately reconstruct the underlying (equilibrium) free energy profile, all from molecular dynamics simulations at a single voltage. The approach developed here applies to other channels that satisfy the conditions of the electrodiffusion equation. PMID:25494790

  7. Molecular structure studies by 3D imaging of fast ion beams

    SciTech Connect

    Kanter, E.P.; Vager, Z.; Both, G.; Cooney, P.J.; Faibis, A.; Koenig, W.; Zabransky, B.J.; Zajfman, D.

    1986-01-01

    The use of the Coulomb-explosion technique combined with a radically new multi-particle detector, extremely thin film targets, and low-excitation ion source has enabled, for the first time, direct measurements of the complete stereochemistry of complex polyatomic molecular ions. We outline the methods used and present results for protonated acetylene (C/sub 2/H/sub 3//sup +/) and the methane cation (CH/sub 4//sup +/) as examples. We demonstrate the techniques by which these methods can be generalized to determine directly vibrational motions in polyatomic molecules. 24 refs., 4 figs.

  8. Cluster secondary ion mass spectrometry and the temperature dependence of molecular depth profiles.

    PubMed

    Mao, Dan; Wucher, Andreas; Brenes, Daniel A; Lu, Caiyan; Winograd, Nicholas

    2012-05-01

    The quality of molecular depth profiles created by erosion of organic materials by cluster ion beams exhibits a strong dependence upon temperature. To elucidate the fundamental nature of this dependence, we employ the Irganox 3114/1010 organic delta-layer reference material as a model system. This delta-layer system is interrogated using a 40 keV C(60)(+) primary ion beam. Parameters associated with the depth profile such as depth resolution, uniformity of sputtering yield, and topography are evaluated between 90 and 300 K using a unique wedge-crater beveling strategy that allows these parameters to be determined as a function of erosion depth from atomic force microscope (AFM) measurements. The results show that the erosion rate calibration performed using the known Δ-layer depth in connection with the fluence needed to reach the peak of the corresponding secondary ion mass spectrometry (SIMS) signal response is misleading. Moreover, we show that the degradation of depth resolution is linked to a decrease of the average erosion rate and the buildup of surface topography in a thermally activated manner. This underlying process starts to influence the depth profile above a threshold temperature between 210 and 250 K for the system studied here. Below that threshold, the process is inhibited and steady-state conditions are reached with constant erosion rate, depth resolution, and molecular secondary ion signals from both the matrix and the Δ-layers. In particular, the results indicate that further reduction of the temperature below 90 K does not lead to further improvement of the depth profile. Above the threshold, the process becomes stronger at higher temperature, leading to an immediate decrease of the molecular secondary ion signals. This signal decay is most pronounced for the highest m/z ions but is less for the smaller m/z ions, indicating a shift toward small fragments by accumulation of chemical damage. The erosion rate decay and surface roughness buildup

  9. Ion Pair in Extreme Aqueous Environments, Molecular-Based and Electric Conductance Approaches

    SciTech Connect

    Chialvo, Ariel A; Gruszkiewicz, Miroslaw {Mirek} S; Simonson, J Michael {Mike}; Palmer, Donald; Cole, David R

    2009-01-01

    We determine by molecular-based simulation the density profiles of the Na+!Cl! ion-pair association constant in steam environments along three supercritical isotherms to interrogate the behavior of ion speciation in dilute aqueous solutions at extreme conditions. Moreover, we describe a new ultra-sensitive flow-through electric conductance apparatus designed to bridge the gap between the currently lowest steam-density conditions at which we are experimentally able to attain electric conductance measurements and the theoretically-reachable zero-density limit. Finally, we highlight important modeling challenges encountered near the zero-density limit and discuss ways to overcome them.

  10. Heterogeneous behavior of metalloproteins toward metal ion binding and selectivity: insights from molecular dynamics studies.

    PubMed

    Gogoi, Prerana; Chandravanshi, Monika; Mandal, Suraj Kumar; Srivastava, Ambuj; Kanaujia, Shankar Prasad

    2016-07-01

    About one-third of the existing proteins require metal ions as cofactors for their catalytic activities and structural complexities. While many of them bind only to a specific metal, others bind to multiple (different) metal ions. However, the exact mechanism of their metal preference has not been deduced to clarity. In this study, we used molecular dynamics (MD) simulations to investigate whether a cognate metal (bound to the structure) can be replaced with other similar metal ions. We have chosen seven different proteins (phospholipase A2, sucrose phosphatase, pyrazinamidase, cysteine dioxygenase (CDO), plastocyanin, monoclonal anti-CD4 antibody Q425, and synaptotagmin 1 C2B domain) bound to seven different divalent metal ions (Ca(2+), Mg(2+), Zn(2+), Fe(2+), Cu(2+), Ba(2+), and Sr(2+), respectively). In total, 49 MD simulations each of 50 ns were performed and each trajectory was analyzed independently. Results demonstrate that in some cases, cognate metal ions can be exchanged with similar metal ions. On the contrary, some proteins show binding affinity specifically to their cognate metal ions. Surprisingly, two proteins CDO and plastocyanin which are known to bind Fe(2+) and Cu(2+), respectively, do not exhibit binding affinity to any metal ion. Furthermore, the study reveals that in some cases, the active site topology remains rigid even without cognate metals, whereas, some require them for their active site stability. Thus, it will be interesting to experimentally verify the accuracy of these observations obtained computationally. Moreover, the study can help in designing novel active sites for proteins to sequester metal ions particularly of toxic nature. PMID:26248730

  11. Adsorption of hydrated halide ions on charged electrodes: Molecular dynamics simulation

    NASA Astrophysics Data System (ADS)

    Glosli, James N.; Philpott, Michael R.

    1993-04-01

    Constant temperature molecular dynamics has been used to simulate the adsorption of hydrated halide ion X(-) = F(-), Cl(-), Br(-), and I(-), and lithium ion Li(+) on a flat uniformly charged surfaces. The simulations were done with either 214 water molecules and two ions (Li(+) and X(-)) in a box 2.362 nm deep or with 430 water molecules and the two ions in a box 4.320 nm deep. The boxes were periodically replicated in the xy directions. The magnitude of the surface charge on the box end was + or - 0.11 c/nm(sup 2), corresponding to an electric field of 2 x 10(exp 7) V/cm. The lateral dimensions of the simulation cell were 1.862 nm x 1.862 nm (x times y) in each case. All of the water molecules and ions interacted with the end walls via a weak 9 - 3 potential. The ST2 water model and parameters optimized for alkali halides interacting with the model ST2 water molecule were used in the calculations. Common practices of truncating the interactions at a finite distance (0.82 nm) and switching off Coulomb interactions at small distances were followed. The temperature was set at T = 2.411 kJ/mole (290 K). Some of the properties calculated were: distribution density profiles for ions and water across the gap important for comparisons iwth Gouy-Chapman theory, adsorbed ion-water pair correlation functions, the number of water molecules in the first and second hydration shells of the ions as a function of time. The time spent by a water molecule in the hydration shell was calculated to be approximately ten times longer for lithium than any other ion. The correlation between distance from the electrode and hydration number was studied and generally found to be pronounced for the larger anions.

  12. Ab initio molecular dynamics simulations of organic electrolytes, electrodes, and lithium ion transport for Li-ion batteries

    NASA Astrophysics Data System (ADS)

    Kent, P. R. C.; Ganesh, P.; Jiang, De-En; Borodin, O.

    2012-02-01

    Optimizing the choice of electrolyte in lithium ion batteries and an understanding of the solid-electrolyte interphase (SEI) is required to optimize the balance between high-energy storage, high rate capability, and lifetime. We perform accurate ab initio molecular-dynamics simulations of common cyclic carbonates and LiPF6 to build solvation models which explain available Neutron and NMR spectroscopies. Our results corroborate why ethylene carbonate is a preferred choice for battery applications over propylene carbonate and how mixtures with dimethyl carbonate improve Li-ion diffusion. We study the role of functionalization of graphite-anode edges on the reducibility of the electrolyte and the ease of Li-ion intercalation at the initial stages of SEI formation. We find that oxygen terminated edges readily act as strong reductive sites, while hydrogen terminated edges are less reactive and allow faster Li diffusion. Orientational ordering of the solvent molecules precedes reduction at the interphase. Inorganic reductive components are seen to readily migrate to the anode edges, leading to increased surface passivation of the anode. We are currently quantifying Li-intercalation barriers across realistic SEI models, and progress along these lines will be presented.

  13. Dipole moments and orientation polarizabilities of diatomic molecular ions for precision atomic mass measurement

    NASA Astrophysics Data System (ADS)

    Cheng, Michelle; Brown, John M.; Rosmus, Pavel; Linguerri, Roberto; Komiha, Najia; Myers, Edmund G.

    2007-01-01

    In high precision Penning trap mass spectrometry the cyclotron frequency of a polarizable ion is perturbed due to the Stark interaction with the motional electric field. For polar diatomic molecular ions, which have adjacent rotational levels of opposite parity, these shifts can be particularly large—especially for the lowest rotational levels, which are those occupied by ions stored for many hours in cryogenic Penning traps. In order to provide corrections to precision atomic mass measurements, we consider the calculation of orientation polarizabilities of CO+ and the positive ions of the first and second row diatomic hydrides, LiH+ to ArH+ . Dipole moments for these ions have been calculated using the restricted coupled cluster method with perturbative triples and large basis sets. Using these dipoles and an effective Hamiltonian, we have obtained rotational-state dependent polarizabilities of the open-shell diatomic ions CO+ , NH+ , OH+ , FH+ , PH+ , SH+ , and ClH+ . Results are given for those rotational levels that are significantly populated at 4.2K , for magnetic fields up to 10T . For the remaining first and second row hydride cations, polarizabilities at the magnetic fields of interest can be obtained from a simple formula valid for closed-shell molecules. Conversely, in cases where the polarizability shifts can be measured, our results enable experimental determination of dipole moments.

  14. Ion transport in the gramicidin channel: molecular dynamics study of single and double occupancy.

    PubMed Central

    Roux, B; Prod'hom, B; Karplus, M

    1995-01-01

    The structural and thermodynamic factors responsible for the singly and doubly occupied saturation states of the gramicidin channel are investigated with molecular dynamics simulations and free energy perturbation methods. The relative free energy of binding of all of the five common cations Li+, Na+, K+, Rb+, and Cs+ is calculated in the singly and doubly occupied channel and in bulk water. The atomic system, which includes the gramicidin channel, a model membrane made of neutral Lennard-Jones particles and 190 explicit water molecules to form the bulk region, is similar to the one used in previous work to calculate the free energy profile of a Na+ ion along the axis of the channel. In all of the calculations, the ions are positioned in the main binding sites located near the entrances of the channel. The calculations reveal that the doubly occupied state is relatively more favorable for the larger ions. Thermodynamic decomposition is used to show that the origin of the trend observed in the calculations is due to the loss of favorable interactions between the ion and the single file water molecules inside the channel. Small ions are better solvated by the internal water molecules in the singly occupied state than in the doubly occupied state; bigger ions are solvated almost as well in both occupation states. Water-channel interactions play a role in the channel response. The observed trends are related to general thermodynamical properties of electrolyte solutions. Images FIGURE 2 PMID:7538804

  15. Ejection of solvated ions from electrosprayed methanol/water nanodroplets studied by molecular dynamics simulations.

    PubMed

    Ahadi, Elias; Konermann, Lars

    2011-06-22

    The ejection of solvated small ions from nanometer-sized droplets plays a central role during electrospray ionization (ESI). Molecular dynamics (MD) simulations can provide insights into the nanodroplet behavior. Earlier MD studies have largely focused on aqueous systems, whereas most practical ESI applications involve the use of organic cosolvents. We conduct simulations on mixed water/methanol droplets that carry excess NH(4)(+) ions. Methanol is found to compromise the H-bonding network, resulting in greatly increased rates of ion ejection and solvent evaporation. Considerable differences in the water and methanol escape rates cause time-dependent changes in droplet composition. Segregation occurs at low methanol concentration, such that layered droplets with a methanol-enriched periphery are formed. This phenomenon will enhance the partitioning of analyte molecules, with possible implications for their ESI efficiencies. Solvated ions are ejected from the tip of surface protrusions. Solvent bridging prior to ion secession is more extensive for methanol/water droplets than for purely aqueous systems. The ejection of solvated NH(4)(+) is visualized as diffusion-mediated escape from a metastable basin. The process involves thermally activated crossing of a ~30 kJ mol(-1) free energy barrier, in close agreement with the predictions of the classical ion evaporation model. PMID:21591733

  16. Molecular dispersion energy parameters for alkali and halide ions in aqueous solution.

    PubMed

    Reiser, S; Deublein, S; Vrabec, J; Hasse, H

    2014-01-28

    Thermodynamic properties of aqueous solutions containing alkali and halide ions are determined by molecular simulation. The following ions are studied: Li(+), Na(+), K(+), Rb(+), Cs(+), F(-), Cl(-), Br(-), and I(-). The employed ion force fields consist of one Lennard-Jones (LJ) site and one concentric point charge with a magnitude of ±1 e. The SPC/E model is used for water. The LJ size parameter of the ion models is taken from Deublein et al. [J. Chem. Phys. 136, 084501 (2012)], while the LJ energy parameter is determined in the present study based on experimental self-diffusion coefficient data of the alkali cations and the halide anions in aqueous solutions as well as the position of the first maximum of the radial distribution function of water around the ions. On the basis of these force field parameters, the electric conductivity, the hydration dynamics of water molecules around the ions, and the enthalpy of hydration is predicted. Considering a wide range of salinity, this study is conducted at temperatures of 293.15 and 298.15 K and a pressure of 1 bar. PMID:25669552

  17. Molecular dispersion energy parameters for alkali and halide ions in aqueous solution

    SciTech Connect

    Reiser, S.; Deublein, S.; Hasse, H.; Vrabec, J.

    2014-01-28

    Thermodynamic properties of aqueous solutions containing alkali and halide ions are determined by molecular simulation. The following ions are studied: Li{sup +}, Na{sup +}, K{sup +}, Rb{sup +}, Cs{sup +}, F{sup −}, Cl{sup −}, Br{sup −}, and I{sup −}. The employed ion force fields consist of one Lennard-Jones (LJ) site and one concentric point charge with a magnitude of ±1 e. The SPC/E model is used for water. The LJ size parameter of the ion models is taken from Deublein et al. [J. Chem. Phys. 136, 084501 (2012)], while the LJ energy parameter is determined in the present study based on experimental self-diffusion coefficient data of the alkali cations and the halide anions in aqueous solutions as well as the position of the first maximum of the radial distribution function of water around the ions. On the basis of these force field parameters, the electric conductivity, the hydration dynamics of water molecules around the ions, and the enthalpy of hydration is predicted. Considering a wide range of salinity, this study is conducted at temperatures of 293.15 and 298.15 K and a pressure of 1 bar.

  18. Molecular dynamics simulations of silicon chloride ion incidence during Si etching in Cl-based plasmas

    NASA Astrophysics Data System (ADS)

    Nakazaki, Nobuya; Takao, Yoshinori; Eriguchi, Koji; Ono, Kouichi

    2014-05-01

    Classical molecular dynamics (MD) simulations have been performed for SiClx+ (x = 0-4) ions incident on Si(100) surfaces, using an improved Stillinger-Weber (SW) potential form, to understand the surface reaction kinetics of etch byproduct ion incidence during Si etching in Cl-based plasmas. The ions were normally incident on surfaces with translational energies in the range of Ei = 20-500 eV, and the surface reaction kinetics of Clx+ (x = 1, 2) ion incidence were also simulated for reference. The etch yields and thresholds presently simulated were in agreement with the experimental results previously reported for the respective ion beam incidences on Si. Numerical results indicated that the etch yields y* per halogen (or per constituent Cl atom of incident ions), thresholds, surface coverages of Cl atoms adsorbed, and thicknesses of chlorinated surface layers are almost the same, when compared at the same translational energy e_{\\text{i}}^{*} per halogen; moreover, the stoichiometries of product species desorbed, stoichiometries of chlorinated surface layers, and their depth profiles are also similar when compared at the same e_{\\text{i}}^{*}. Thus, it follows that the etching characteristics for SiClx+ as well as Clx+ incidences on Si are determined primarily or scaled universally by e_{\\text{i}}^{*}, unless the deposition is significant at low Ei or e_{\\text{i}}^{*} for SiCl+ and SiCl2+.

  19. Promoting the Adsorption of Metal Ions on Kaolinite by Defect Sites: A Molecular Dynamics Study

    PubMed Central

    Li, Xiong; Li, Hang; Yang, Gang

    2015-01-01

    Defect sites exist abundantly in minerals and play a crucial role for a variety of important processes. Here molecular dynamics simulations are used to comprehensively investigate the adsorption behaviors, stabilities and mechanisms of metal ions on defective minerals, considering different ionic concentrations, defect sizes and contents. Outer-sphere adsorbed Pb2+ ions predominate for all models (regular and defective), while inner-sphere Na+ ions, which exist sporadically only at concentrated solutions for regular models, govern the adsorption for all defective models. Adsorption quantities and stabilities of metal ions on kaolinite are fundamentally promoted by defect sites, thus explaining the experimental observations. Defect sites improve the stabilities of both inner- and outer-sphere adsorption, and (quasi) inner-sphere Pb2+ ions emerge only at defect sites that reinforce the interactions. Adsorption configurations are greatly altered by defect sites but respond weakly by changing defect sizes or contents. Both adsorption quantities and stabilities are enhanced by increasing defect sizes or contents, while ionic concentrations mainly affect adsorption quantities. We also find that adsorption of metal ions and anions can be promoted by each other and proceeds in a collaborative mechanism. Results thus obtained are beneficial to comprehend related processes for all types of minerals. PMID:26403873

  20. A Novel Methodology for Metal Ion Separation Based on Molecularly Imprinting

    SciTech Connect

    Zuo, Xiaobin; Mosha, Donnati; Hassan, Mansour M.; Givens, Richard S.; Busch, Daryle H.

    2004-03-31

    The siderophore-based extraction of iron from the soil by bacteria is proposed as a model for a new separation methodology labeled the soil poutice, a molecular device that would selectively retrieve the complex of a targeted metal ion. In this report we described the synthesis and characterization of molecularly imprinted polymers and their application in the specific recognition of macrocyclic metal complexes. The imprinting is based on non-covalent interactions such as hydrogen bonding, electrostatic attractions and minor metal-ligand coordination. Good rebinding capacity for the imprinting metal complex was observed in acetonitrile as well as in water. The polymers are resistant to strong acids and oxidizing agents and showed an increase of rebinding capacity during cycles of reuse. The imprinting procedure, combined with the previously known selective chelation of macrocyclic ligands, supports the feasibility of a new methodology that can be used to extract waste metal ions effectively and selectively from soils and ground water.

  1. Confinement of the hydrogen molecular ion H2+ under a magnetic field inside a spheroid

    NASA Astrophysics Data System (ADS)

    Molinar, Martin

    2010-03-01

    A study of the confinement of the hydrogen molecular ion H2+ is done. The molecular ion is subject to the action of a magnetic field. In the Born -- Oppenheimer approximation, we solve numerically the Schr"odinger's equation, using trial functions and one algorithm that allows us to calculate the energies for different given values of the confinement parameters. We use the variational method in order to estimate the energy of the ground state. Some properties of the system as the pressure exerted by the confinement, the polarizability in the approximations of Kirkwood and Buckingham and the energies of the vibrational states are calculated. The behavior of the internuclear separation is analyzed for the geometry considered.

  2. Coupling all-atom molecular dynamics simulations of ions in water with Brownian dynamics

    PubMed Central

    2016-01-01

    Molecular dynamics (MD) simulations of ions (K+, Na+, Ca2+ and Cl−) in aqueous solutions are investigated. Water is described using the SPC/E model. A stochastic coarse-grained description for ion behaviour is presented and parametrized using MD simulations. It is given as a system of coupled stochastic and ordinary differential equations, describing the ion position, velocity and acceleration. The stochastic coarse-grained model provides an intermediate description between all-atom MD simulations and Brownian dynamics (BD) models. It is used to develop a multiscale method which uses all-atom MD simulations in parts of the computational domain and (less detailed) BD simulations in the remainder of the domain. PMID:27118886

  3. Molecular ion-pair states in ungerade H{sub 2}

    SciTech Connect

    Kirrander, Adam; Jungen, Christian

    2011-11-15

    Molecular ion-pair states are analogs of electronic Rydberg states, but with the electron replaced by a much heavier ion. We calculate ab initio the long-range vibrational H{sup +}H{sup -} ion-pair states in H{sub 2} for ungerade {sup 1}{Sigma}{sub u}{sup +} symmetry, corresponding to recent observations by Ekey and McCormack [Phys. Rev. A 84, 020501 (2011)]. The overall trends in the experiment are reproduced and many peaks can be assigned. The calculations yield interloper resonances corresponding to vibrational states trapped inside the barriers on the potential-energy curves 5,6 {sup 1}{Sigma}{sub u}{sup +}.

  4. Crystal structures reveal the molecular basis of ion translocation in sodium/proton antiporters.

    PubMed

    Coincon, Mathieu; Uzdavinys, Povilas; Nji, Emmanuel; Dotson, David L; Winkelmann, Iven; Abdul-Hussein, Saba; Cameron, Alexander D; Beckstein, Oliver; Drew, David

    2016-03-01

    To fully understand the transport mechanism of Na(+)/H(+) exchangers, it is necessary to clearly establish the global rearrangements required to facilitate ion translocation. Currently, two different transport models have been proposed. Some reports have suggested that structural isomerization is achieved through large elevator-like rearrangements similar to those seen in the structurally unrelated sodium-coupled glutamate-transporter homolog GltPh. Others have proposed that only small domain movements are required for ion exchange, and a conventional rocking-bundle model has been proposed instead. Here, to resolve these differences, we report atomic-resolution structures of the same Na(+)/H(+) antiporter (NapA from Thermus thermophilus) in both outward- and inward-facing conformations. These data combined with cross-linking, molecular dynamics simulations and isothermal calorimetry suggest that Na(+)/H(+) antiporters provide alternating access to the ion-binding site by using elevator-like structural transitions. PMID:26828964

  5. A SEARCH FOR CO-EVOLVING ION AND NEUTRAL GAS SPECIES IN PRESTELLAR MOLECULAR CLOUD CORES

    SciTech Connect

    Tassis, Konstantinos; Hezareh, Talayeh; Willacy, Karen

    2012-11-20

    A comparison between the widths of ion and neutral molecule spectral lines has been recently used to estimate the strength of the magnetic field in turbulent star-forming regions. However, the ion (HCO{sup +}) and neutral (HCN) species used in such studies may not be necessarily co-evolving at every scale and density, and thus, may not trace the same regions. Here, we use coupled chemical/dynamical models of evolving prestellar molecular cloud cores including non-equilibrium chemistry, with and without magnetic fields, to study the spatial distribution of HCO{sup +} and HCN, which have been used in observations of spectral line width differences to date. In addition, we seek new ion-neutral pairs that are good candidates for such observations, because they have similar evolution and are approximately co-spatial in our models. We identify three such good candidate pairs: HCO{sup +}/NO, HCO{sup +}/CO, and NO{sup +}/NO.

  6. Nonlinear effects in defect production by atomic and molecular ion implantation

    NASA Astrophysics Data System (ADS)

    David, C.; Varghese Anto, C.; Dholakia, Manan; Chandra, Sharat; Nair, K. G. M.; Panigrahi, B. K.; Santhana Raman, P.; Amirthapandian, S.; Amarendra, G.; Kennedy, John

    2015-01-01

    This report deals with studies concerning vacancy related defects created in silicon due to implantation of 200 keV per atom aluminium and its molecular ions up to a plurality of 4. The depth profiles of vacancy defects in samples in their as implanted condition are carried out by Doppler broadening spectroscopy using low energy positron beams. In contrast to studies in the literature reporting a progressive increase in damage with plurality, implantation of aluminium atomic and molecular ions up to Al3, resulted in production of similar concentration of vacancy defects. However, a drastic increase in vacancy defects is observed due to Al4 implantation. The observed behavioural trend with respect to plurality has even translated to the number of vacancies locked in vacancy clusters, as determined through gold labelling experiments. The impact of aluminium atomic and molecular ions simulated using MD showed a monotonic increase in production of vacancy defects for cluster sizes up to 4. The trend in damage production with plurality has been explained on the basis of a defect evolution scheme in which for medium defect concentrations, there is a saturation of the as-implanted damage and an increase for higher defect concentrations.

  7. Nonlinear effects in defect production by atomic and molecular ion implantation

    SciTech Connect

    David, C. Dholakia, Manan; Chandra, Sharat; Nair, K. G. M.; Panigrahi, B. K.; Amirthapandian, S.; Amarendra, G.; Varghese Anto, C.; Santhana Raman, P.; Kennedy, John

    2015-01-07

    This report deals with studies concerning vacancy related defects created in silicon due to implantation of 200 keV per atom aluminium and its molecular ions up to a plurality of 4. The depth profiles of vacancy defects in samples in their as implanted condition are carried out by Doppler broadening spectroscopy using low energy positron beams. In contrast to studies in the literature reporting a progressive increase in damage with plurality, implantation of aluminium atomic and molecular ions up to Al{sub 3}, resulted in production of similar concentration of vacancy defects. However, a drastic increase in vacancy defects is observed due to Al{sub 4} implantation. The observed behavioural trend with respect to plurality has even translated to the number of vacancies locked in vacancy clusters, as determined through gold labelling experiments. The impact of aluminium atomic and molecular ions simulated using MD showed a monotonic increase in production of vacancy defects for cluster sizes up to 4. The trend in damage production with plurality has been explained on the basis of a defect evolution scheme in which for medium defect concentrations, there is a saturation of the as-implanted damage and an increase for higher defect concentrations.

  8. Molecular Dynamics Simulation of the Antiamoebin Ion Channel: Linking Structure and Conductance

    NASA Technical Reports Server (NTRS)

    Wilson, Michael A.; Wei, Chenyu; Bjelkmar, Paer; Wallace, B. A.; Pohorille, Andrew

    2011-01-01

    Molecular dynamics simulations were carried out in order to ascertain which of the potential multimeric forms of the transmembrane peptaibol channel, antiamoebin, is consistant with its measured conductance. Estimates of the conductance obtained through counting ions that cross the channel and by solving the Nernst-Planck equation yield consistent results, indicating that the motion of ions inside the channel can be satisfactorily described as diffusive.The calculated conductance of octameric channels is markedly higher than the conductance measured in single channel recordings, whereas the tetramer appears to be non-conducting. The conductance of the hexamer was estimated to be 115+/-34 pS and 74+/-20 pS, at 150 mV and 75 mV, respectively, in satisfactory agreement with the value of 90 pS measured at 75 mV. On this basis we propose that the antiamoebin channel consists of six monomers. Its pore is large enough to accommodate K(+) and Cl(-) with their first solvation shells intact. The free energy barrier encountered by K(+) is only 2.2 kcal/mol whereas Cl(-) encounters a substantially higher barrier of nearly 5 kcal/mol. This difference makes the channel selective for cations. Ion crossing events are shown to be uncorrelated and follow Poisson statistics. keywords: ion channels, peptaibols, channel conductance, molecular dynamics

  9. Complexation of tetrandrine with calcium ion probed by various spectroscopic methods and molecular modeling

    NASA Astrophysics Data System (ADS)

    Stanculescu, Ioana; Mandravel, Cristina; Landy, David; Woisel, Patrice; Surpateanu, Gheorghe

    2003-07-01

    The formation of the complex between tetrandrine and the calcium ion, in solution, was studied using FTIR, UV-Vis, 1H NMR, 13C NMR and electrospray mass spectroscopy spectroscopic methods and molecular modeling. The calcium salts used were: Ca(ClO 4) 2·4H 2O and Ca(Picrate) 2 in the solvents: acetonitrile (CH 3CN), deuterated acetonitrile (CD 3CN) and tetrahydrofurane (THF). The determined complex stability constant was: 20277±67 dm 3 mol -1 and corresponding free energy Δ G0=-5.820±0.002 kcal mol -1. The molecular simulation of the complex formation with the MM3 Augmented force field integrated in CAChe provided useful data about its energy. Combining the experimental results and molecular modeling we propose a model for the structure of tetrandrine-Ca complex with an eight coordinated geometry.

  10. Effect of molecular weight on ion diffusion and transference number in poly(ethylene oxide)

    NASA Astrophysics Data System (ADS)

    Timachova, Ksenia; Balsara, Nitash

    2015-03-01

    Solid polymer electrolytes are of great interest for their potential use in high specific energy, solid-state batteries, however, salt transport properties in polymer electrolytes have not been comprehensively addressed over a wide range of molecular weights. Poly(ethylene oxide) (PEO) has been the most widely studied polymer electrolyte due to its high solvation of lithium salts and low glass transition temperature. This study presents measurements of the transport properties of lithium bis(trifluoromethanesulfone)imide (LiTFSI) in PEO at both the high concentration present in functional electrolytes and in the dilute limit for a large range of PEO molecular weights. Individual diffusion coefficients of the Li + and TFSI- ions were measured using pulsed-field gradient nuclear magnetic resonance and the cation transference number was calculated. The diffusion coefficients, transference number, and conductivity as a function of molecular weight and salt concentration provide a complete set of transport properties for PEO.