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Sample records for molecular photoionization measured

  1. Photoionization of molecular clusters

    NASA Astrophysics Data System (ADS)

    Andres, R. P.; Calo, J. M.

    1981-12-01

    An experimental apparatus consisting of a novel multiple expansion cluster source coupled with a molecular beam system and photoionization mass spectrometer has been designed and constructed. This apparatus has been thoroughly tested and preliminary measurements of the growth kinetics of water clusters and the photoionization cross section of the water dimer have been carried out.

  2. Photoelectron photoion molecular beam spectroscopy

    SciTech Connect

    Trevor, D.J.

    1980-12-01

    The use of supersonic molecular beams in photoionization mass spectroscopy and photoelectron spectroscopy to assist in the understanding of photoexcitation in the vacuum ultraviolet is described. Rotational relaxation and condensation due to supersonic expansion were shown to offer new possibilities for molecular photoionization studies. Molecular beam photoionization mass spectroscopy has been extended above 21 eV photon energy by the use of Stanford Synchrotron Radiation Laboratory (SSRL) facilities. Design considerations are discussed that have advanced the state-of-the-art in high resolution vuv photoelectron spectroscopy. To extend gas-phase studies to 160 eV photon energy, a windowless vuv-xuv beam line design is proposed.

  3. Theory of attosecond delays in molecular photoionization

    NASA Astrophysics Data System (ADS)

    Baykusheva, Denitsa; Wörner, Hans Jakob

    2017-03-01

    We present a theoretical formalism for the calculation of attosecond delays in molecular photoionization. It is shown how delays relevant to one-photon-ionization, also known as Eisenbud-Wigner-Smith delays, can be obtained from the complex dipole matrix elements provided by molecular quantum scattering theory. These results are used to derive formulae for the delays measured by two-photon attosecond interferometry based on an attosecond pulse train and a dressing femtosecond infrared pulse. These effective delays are first expressed in the molecular frame where maximal information about the molecular photoionization dynamics is available. The effects of averaging over the emission direction of the electron and the molecular orientation are introduced analytically. We illustrate this general formalism for the case of two polyatomic molecules. N2O serves as an example of a polar linear molecule characterized by complex photoionization dynamics resulting from the presence of molecular shape resonances. H2O illustrates the case of a non-linear molecule with comparably simple photoionization dynamics resulting from a flat continuum. Our theory establishes the foundation for interpreting measurements of the photoionization dynamics of all molecules by attosecond metrology.

  4. Photoionization of aligned molecular excited states

    NASA Astrophysics Data System (ADS)

    Appling, J. R.; White, M. G.; Kessler, W. J.; Fernandez, R.; Poliakoff, E. D.

    1988-02-01

    Photoelectron angular distributions of several excited states of NO have been measured in an effort to better elucidate the role of alignment in resonant multiphoton excitation processes of molecules. In contrast to previous molecular REMPI measurements on NO, (2+1) angular distributions taken for low rotational levels of the E 2Σ+ (4sσ) Rydberg state of NO exhibit complex angular behavior which is characteristic of strong spatial alignment of the optically prepared levels. Photoelectron angular distributions were also found to be strongly branch and J dependent with the lowest rotational levels of the R21+S11 branch exhibiting the full anisotropy expected for an overall three-photon process. Fluorescence anisotropies extracted from complementary two-photon fluorescence angular distribution measurements reveal small, but nonzero alignment in all rotational levels with J>1/2, in contrast to the photoelectron results. Additional photoelectron angular distributions taken for (1+1) REMPI via the A 2Σ+ (3sσ), v=0 state exhibit near ``cos2θ'' distributions characteristic of photoionization of unaligned target states. The observed photoelectron data are qualitatively interpreted on the basis of the angular momentum constraints of the excitation-induced alignment and photoionization dynamics which determine the observable moments in the angular distribution.

  5. Electron localization following attosecond molecular photoionization.

    PubMed

    Sansone, G; Kelkensberg, F; Pérez-Torres, J F; Morales, F; Kling, M F; Siu, W; Ghafur, O; Johnsson, P; Swoboda, M; Benedetti, E; Ferrari, F; Lépine, F; Sanz-Vicario, J L; Zherebtsov, S; Znakovskaya, I; L'huillier, A; Ivanov, M Yu; Nisoli, M; Martín, F; Vrakking, M J J

    2010-06-10

    For the past several decades, we have been able to directly probe the motion of atoms that is associated with chemical transformations and which occurs on the femtosecond (10(-15)-s) timescale. However, studying the inner workings of atoms and molecules on the electronic timescale has become possible only with the recent development of isolated attosecond (10(-18)-s) laser pulses. Such pulses have been used to investigate atomic photoexcitation and photoionization and electron dynamics in solids, and in molecules could help explore the prompt charge redistribution and localization that accompany photoexcitation processes. In recent work, the dissociative ionization of H(2) and D(2) was monitored on femtosecond timescales and controlled using few-cycle near-infrared laser pulses. Here we report a molecular attosecond pump-probe experiment based on that work: H(2) and D(2) are dissociatively ionized by a sequence comprising an isolated attosecond ultraviolet pulse and an intense few-cycle infrared pulse, and a localization of the electronic charge distribution within the molecule is measured that depends-with attosecond time resolution-on the delay between the pump and probe pulses. The localization occurs by means of two mechanisms, where the infrared laser influences the photoionization or the dissociation of the molecular ion. In the first case, charge localization arises from quantum mechanical interference involving autoionizing states and the laser-altered wavefunction of the departing electron. In the second case, charge localization arises owing to laser-driven population transfer between different electronic states of the molecular ion. These results establish attosecond pump-probe strategies as a powerful tool for investigating the complex molecular dynamics that result from the coupling between electronic and nuclear motions beyond the usual Born-Oppenheimer approximation.

  6. Rotational distributions of molecular photoions following resonant excitation

    NASA Astrophysics Data System (ADS)

    Poliakoff, E. D.; Chan, Jeffrey C. K.; White, M. G.

    1986-11-01

    We demonstrate that the photoelectron energy mediates the rotational energy distribution of N+2 ions created by photoionization, and conversely, that rotational energy determinations probe resonant excitation in molecular photoionization. Experimentally, this is accomplished by monitoring the dispersed fluorescence from N+2 (B 2Σ+u) photoions to determine their rotational energy distribution. These results demonstrate that while dipole selection rules constrain the total angular momentum of the electron-ion complex, the partitioning of angular momentum between the photoelectron and photoion depends on the photoejection dynamics. Implications for photoionization and electron impact ionizatin studies are discussed.

  7. Franck—Condon breakdown as a probe of continuum coupling in molecular photoionization

    NASA Astrophysics Data System (ADS)

    Kakar, Sandeep; Choi, Heung Cheun; Poliakoff, E. D.

    1992-03-01

    We have measured vibrational branching ratios for 4σ -1 photoionization of CO in order to characterize continuum channel coupling. The results indicate that the shape resonance in the 5σ→ɛσ channel influences vibrational branching ratios of the 4σ -1 channel via continuum coupling, and the data illustrate how continuum channel coupling affects molecular photoionization dynamics.

  8. Dissociation Dynamics and Molecular Imaging of Methane following Photoionization at the Carbon K-Edge

    NASA Astrophysics Data System (ADS)

    Williams, J. B.; Trevisan, C.; Schoeffler, M. S.; Jahnke, T.; Bocharova, I.; Sturm, F.; McCurdy, C. W.; Belkacem, A.; Doerner, R.; Weber, Th; Landers, A. L.

    2014-04-01

    We have used Cold Target Recoil Ion Momentum Spectroscopy (COLTRIMS) to measure the momenta of the photoelectron and the molecular fragments arising from the dissociation of methane following core photoionization and subsequent Auger decay.

  9. Double Photoionization of Aligned Molecular Hydrogen

    SciTech Connect

    Vanroose, Wim; Horner, Daniel A.; Martin, Fernando; Rescigno,Thomas N.; McCurdy, C. William

    2006-07-21

    We present converged, completely ab initio calculations ofthe triple differential cross sections for double photoionization ofaligned H2 molecules for a photon energy of 75.0 eV. The method ofexterior complex scaling, implemented with both the discrete variablerepresentation and B-splines, is used to solve the Schroedinger equationfor a correlated continuum wave function corresponding to a single photonhaving been absorbed by a correlated initial state. Results for a fixedinternuclear distance are compared with recent experiments and show thatintegration over experimental angular and energy resolutions is necessaryto produce good qualitative agreement, but does not eliminate somediscrepancies. Limitations of current experimental resolution are shownto sometimes obscure interesting details of the crosssection.

  10. Molecular photoionization studies of nucleobases and correlated systems

    SciTech Connect

    Poliakoff, Erwin D.

    2015-03-11

    We proposed molecular photoionization studies in order to probe correlated events in fundamental scattering phenomena. In particular, we suggested that joint theoretical-experimental studies would provide a window into the microscopic aspects that are of central importance in AMO and chemical physics generally, and would generate useful data for wide array of important DOE topics, such as ultrafast dynamics, high harmonic generation, and probes of nonadiabatic processes. The unifying theme is that correlations between electron scattering dynamics and molecular geometry highlight inherently molecular aspects of the photoelectron behavior.

  11. Vibrationally mode-specific excitation in molecular photoionization

    NASA Astrophysics Data System (ADS)

    Poliakoff, Erwin

    2003-05-01

    Recent measurements on the photoionization of polyatomic molecules demonstrate that excitations of nominally forbidden vibrations are surprisingly intense, and that their energy dependences elucidate why they are occurring. The unifying theme underscored by these results is that the continuum photoelectron exerts tremendous influence on which vibrations are excited and the degree of excitation. These data are generated via high resolution photoelectron spectroscopy coupled with high brightness synchrotron radiation. Results are presented on the linear triatomic systems CO_2, CS_2, and N_2O. For these molecules, all vibrational modes are excited. Moreover, the energy dependences for the alternative vibrational modes exhibit dramatic differences, which are attributed to the degree and type of localization experienced by the continuum photoelectron in the molecular framework. And while the electronic structures of these molecules are very similar, they behave very differently from each other, even over a very broad energy range. Theoretical results by Prof. R.R. Lucchese will be discussed, and the comparison with experiment helps to illustrate the state of our understanding of these phenomena. In addition to the linear triatomics, preliminary results will be reported on BF_3, as well as a van der Waals dimer, Ar_2.

  12. Absolute measurements of chlorine Cl+ cation single photoionization cross section

    NASA Astrophysics Data System (ADS)

    Hernández, E. M.; Juárez, A. M.; Kilcoyne, A. L. D.; Aguilar, A.; Hernández, L.; Antillón, A.; Macaluso, D.; Morales-Mori, A.; González-Magaña, O.; Hanstorp, D.; Covington, A. M.; Davis, V.; Calabrese, D.; Hinojosa, G.

    2015-01-01

    The photoionization of Cl+ leading to Cl2+ was measured in the photon energy range of 19.5-28.0 eV. A spectrum with a photon energy resolution of 15 meV normalized to absolute cross-section measurements is presented. The measurements were carried out by merging a Cl+ ion beam with a photon beam of highly monochromatic synchrotron radiation at the Advanced Light Source at Lawrence Berkeley National Laboratory. The measured photoionization of Cl+ consists of several autoionization resonances surperimposed on the direct photoionization signal. Most of the prominent resonances are assigned to members of Rydberg series originating from the singlet ground state and from metastable triplet levels within the ground-state configuration of Cl+. The direct ionization cross section is no larger than 12 Mb.

  13. Turbulence in giant molecular clouds: the effect of photoionization feedback

    NASA Astrophysics Data System (ADS)

    Boneberg, D. M.; Dale, J. E.; Girichidis, P.; Ercolano, B.

    2015-02-01

    Giant molecular clouds (GMCs) are observed to be turbulent, but theory shows that without a driving mechanism turbulence should quickly decay. The question arises by which mechanisms turbulence is driven or sustained. It has been shown that photoionizing feedback from massive stars has an impact on the surrounding GMC and can for example create vast H II bubbles. We therefore address the question of whether turbulence is a consequence of this effect of feedback on the cloud. To investigate this, we analyse the velocity field of simulations of high-mass star-forming regions by studying velocity structure functions and power spectra. We find that clouds whose morphology is strongly affected by photoionizing feedback also show evidence of driving of turbulence by preserving or recovering a Kolmogorov-type velocity field. On the contrary, control run simulations without photoionizing feedback have a velocity distribution that bears the signature of gravitational collapse and of the dissipation of energy, where the initial Kolmogorov-type structure function is erased.

  14. Fluorescence probes of spectroscopic and dynamical aspects of molecular photoionization

    NASA Astrophysics Data System (ADS)

    Poliakoff, Erwin D.

    1988-11-01

    Studies were made of vibrationally resolved aspects of shape resonant excitation in the photoionization of N(2)0. This experiment was performed by generating dispersed fluorescence spectra from electronically excited photoions. These results are the first vibrationally resolved results on a polyatomic shape resonance. In vibrationally resolved measurements, different internuclear configurations are probed by sampling alternative vibrational levels of the ion. As a result, the continuum electron behavior can be mapped out most clearly, and the qualitative aspects of the electron ejection can be understood clearly. A central motivation for studying polyatomic shape resonances is that alternative vibrational modes may be explored, revealing facets that are nonexistent for diatomic systems, which are the only systems that have been characterized previously.

  15. Short-time Chebyshev wave packet method for molecular photoionization

    NASA Astrophysics Data System (ADS)

    Sun, Zhaopeng; Zheng, Yujun

    2016-08-01

    In this letter we present the extended usage of short-time Chebyshev wave packet method in the laser induced molecular photoionization dynamics. In our extension, the polynomial expansion of the exponential in the time evolution operator, the Hamiltonian operator can act on the wave packet directly which neatly avoids the matrix diagonalization. This propagation scheme is of obvious advantages when the dynamical system has large Hamiltonian matrix. Computational simulations are performed for the calculation of photoelectronic distributions from intense short pulse ionization of K2 and NaI which represent the Born-Oppenheimer (BO) model and Non-BO one, respectively.

  16. Measurement of photoionization cross sections of the excited states of titanium, cobalt, and nickel

    SciTech Connect

    Cong Ran; Cheng Yi; Yang Jiajun; Fan Jianmei; Yao Guanxin; Ji Xuehan; Zheng Xianfeng; Cui Zhifeng

    2009-07-01

    Resonance-enhanced multiphoton ionization (REMPI) of Ti, Co, and Ni atoms has been investigated in the 285-320 nm region. We couple a laser-ablated metal target into a molecular beam to produce atoms. Ions produced from photoionization of the neutral atoms are monitored by a home-built time-of-flight mass spectrometer. Photoionization cross sections of the excited states of Ti, Co, and Ni were deduced from the dependence of the ion signal intensity on the laser intensity for photon energies close to the ionization threshold. The values obtained range from 0.2 to 6.0 Mb. No significant isotope dependence was found from measurements of the photoionization cross sections of {sup 46}Ti, {sup 47}Ti, {sup 48}Ti, {sup 58}Ni, and {sup 60}Ni.

  17. Global Franck-Condon breakdown: nonresonant molecular photoionization processes

    NASA Astrophysics Data System (ADS)

    Das, Aloke; Hardy, David; Aguilar, Alejandro; Kilcoyne, A. L. D.; Bozek, John D.; Poliakoff, Erwin D.

    2007-06-01

    We report photoelectron spectroscopy results of nonresonant Franck-Condon breakdown in the photoionization of CO and ICN. Most importantly, the deviations occur over a surprisingly wide range of energies. For the case of CO^+(X^2σ^+), the v^ + = 1/v^ + = 0 vibrational branching ratio is found to vary significantly (>50%) over a 200 eV range. While it is well understood that resonances can lead to coupling between photoelectron and molecular vibration, there is little information on nonresonant sources of coupling. It appears that Cooper minima may be responsible for the observations. Moreover, for ICN, the vibrationally resolved deviations from Franck-Condon behavior are vibrationally mode-specific. Studies on alternative molecular targets are planned to see whether they exhibit photoelectron dynamics that are geometry-dependent.

  18. Precision measurements on the photoionization of neutral atomic species

    NASA Astrophysics Data System (ADS)

    Stolte, Wayne

    2016-05-01

    In contrast to studies on rare gas atoms, experimental studies of open-shell atoms offers very challenging problems, such as creation of the atom, low signal, purity and stability. Because of this, studies of inner-shell excitations for open shell atoms are limited. In this talk I will discuss precision experimental measurements for photoionization of atomic oxygen, nitrogen, and chlorine over the last two decades on various beamlines at Lawrence Berkeley National Laboratories, Advanced Light Source.

  19. Measurements of isotope effects in the photoionization of N2 and implications for Titan's atmosphere

    SciTech Connect

    Croteau, Philip; Randazzo, John B.; Kostko, Oleg; Ahmed, Musahid; Liang, Mao-Chang; Yung, Yuk L.; Boering, Kristie A.

    2010-12-30

    Isotope effects in the non-dissociative photoionization of molecular nitrogen (N2 + h nu -> N2+ + e-) may play a role in determining the relative abundances of isotopic species containing nitrogen in interstellar clouds and planetary atmospheres but have not been previously measured. Measurements of the photoionization efficiency spectra of 14N2, 15N14N, and 15N2 from 15.5 to 18.9 eV (65.6-80.0 nm) using the Advanced Light Source at Lawrence Berkeley National Laboratory show large differences in peak energies and intensities, with the ratio of the energy-dependent photoionization cross-sections, sigma(14N2)/sigma(15N14N), ranging from 0.4 to 3.5. Convolving the cross-sections with the solar flux and integrating over the energies measured, the ratios of photoionization rate coefficients are J(15N14N)/J(14N2)=1.00+-0.02 and J(15N2)/J(14N2)=1.00+-0.02, suggesting that isotopic fractionation between N2 and N2+ should be small under such conditions. In contrast, in a one-dimensional model of Titan's atmosphere, isotopic self-shielding of 14N2 leads to values of J(15N14N)/J(14N2) as large as ~;;1.17, larger than under optically thin conditions but still much smaller than values as high as ~;;29 predicted for N2 photodissociation. Since modeled photodissociation isotope effects overpredict the HC15N/HC14N ratio in Titan's atmosphere, and since both N atoms and N2+ ions may ultimately lead to the formation of HCN, estimates of the potential of including N2 photoionization to contribute to a more quantitative explanation of 15N/14N for HCN in Titan's atmosphere are explored.

  20. Using vibrational branching ratios to probe shape resonances in molecular photoionization

    NASA Astrophysics Data System (ADS)

    Lucchese, Robert; Das, Aloke; Poliakoff, Erwin; Bozek, John

    2009-05-01

    The measurement of vibrational branching ratios in molecular photoionization can be used as a probe of the nature of resonant states, since such states are often sensitive to the geometry of the molecule. Recent computed results for BF3 and C6F6 will be presented. In C6F6, we consider the excitation of the two symmetric stretching modes in the photoionization leading to the C ^3B2u state of the ion. Two prominent shape resonances at photon energies between 18 and 20 eV respond quite differently to the excitation of the symmetric ring-breathing mode and to the symmetric C-F stretching mode. In BF3, the excitation of both the symmetric stretching and the degenerate asymmetric stretching modes are considered in the photoionization leading to the E ^2A1' state of the ion. The symmetric stretching mode shows a relatively weak resonant enhancement in the branching ratio, whereas the asymmetric stretching mode has a much more prominent feature.

  1. Photoionization cross section measurements of the excited states of cobalt in the near-threshold region

    SciTech Connect

    Zheng, Xianfeng Zhou, Xiaoyu; Cheng, Zaiqi; Jia, Dandan; Qu, Zehua; Yao, Guanxin; Zhang, Xianyi; Cui, Zhifeng

    2014-10-15

    We present measurements of photoionization cross-sections of the excited states of cobalt using a two-color, two-step resonance ionization technique in conjunction with a molecular beam time of flight (TOF) mass spectrometer. The atoms were produced by the laser vaporization of a cobalt rod, coupled with a supersonic gas jet. The absolute photoionization cross-sections at threshold and near-threshold regions (0-1.2 eV) were measured, and the measured values ranged from 4.2±0.7 Mb to 10.5±1.8 Mb. The lifetimes of four odd parity energy levels are reported for the first time.

  2. Ionic photofragmentation and photoionization of dimethyl ether in the VUV and soft X-ray regions (8.5 80 eV) absolute oscillator strengths for molecular and dissociative photoionization

    NASA Astrophysics Data System (ADS)

    Feng, Renfei; Cooper, Glyn; Brion, C. E.

    2001-08-01

    The branching ratios for molecular and dissociative photoionization of dimethyl ether (CH 3OCH 3, DME) have been measured in the VUV and soft X-ray regions using dipole (e,e+ion) coincidence spectroscopy (˜1 eV FWHM) at equivalent photon energies from the first ionization threshold up to 80 eV. The absolute partial oscillator strengths (cross-sections) for molecular and dissociative photoionization have been determined from recently published absolute photoabsorption oscillator strength data [R. Feng, G. Cooper, C.E. Brion, Chem. Phys. 260 (2000) 391] together with the photoionization branching ratios and the (multi-dissociative-corrected) photoionization efficiency obtained from time-of-flight mass spectra reported in the present work. No stable multiply charged molecular ion(s) from DME have been found in the present work. However, the fact that the photoionization efficiency has been measured as greater than unity above ˜30 eV indicates the existence of multi-dissociative products from Coulomb explosion of multiply charged ions. Appearance potentials of all ion products from DME are also reported. The presently reported results are compared with the previously published data where possible.

  3. Cross sections for photoionization of fullerene molecular ions C n + with n = 40, 50, 70, 76, 78, and 84

    NASA Astrophysics Data System (ADS)

    Thomas, C. M.; Baral, K. K.; Aryal, N. B.; Habibi, M.; Esteves-Macaluso, D. A.; Kilcoyne, A. L. D.; Aguilar, A.; Schlachter, A. S.; Schippers, S.; Müller, A.; Phaneuf, R. A.

    2017-05-01

    Absolute cross-section measurements are reported for single photoionization of C n + fullerene molecular ions (n =40 , 50, 70, 76, 78, and 84) in the photon-energy range 18-70 eV. The experiments were performed by merging a mass and charge selected beam of C n + molecular ions with a beam of monochromatized synchrotron radiation and measuring the yield of C n 2 + product ions as a function of the photon energy. Oscillator strengths determined by integrating the measured cross sections over this energy range exhibit a linear dependence on n . The cross sections are parametrized by fits to three Lorentzian functions to represent plasmon excitations and a linear function for direct ionization. The highest-energy resonance in the data near 46 eV is similar to that previously observed in single photoionization of C60 and may be attributable to a harmonic of the dominant surface-plasmon resonance near 23 eV.

  4. Retrieving transient conformational molecular structure information from inner-shell photoionization of laser-aligned molecules

    SciTech Connect

    Wang, Xu; Le, Anh -Thu; Yu, Chao; Lucchese, R. R.; Lin, C. D.

    2016-03-30

    We discuss a scheme to retrieve transient conformational molecular structure information using photoelectron angular distributions (PADs) that have averaged over partial alignments of isolated molecules. The photoelectron is pulled out from a localized inner-shell molecular orbital by an X-ray photon. We show that a transient change in the atomic positions from their equilibrium will lead to a sensitive change in the alignment-averaged PADs, which can be measured and used to retrieve the former. Exploiting the experimental convenience of changing the photon polarization direction, we show that it is advantageous to use PADs obtained from multiple photon polarization directions. Lastly, a simple single-scattering model is proposed and benchmarked to describe the photoionization process and to do the retrieval using a multiple-parameter fitting method.

  5. Retrieving transient conformational molecular structure information from inner-shell photoionization of laser-aligned molecules

    DOE PAGES

    Wang, Xu; Le, Anh -Thu; Yu, Chao; ...

    2016-03-30

    We discuss a scheme to retrieve transient conformational molecular structure information using photoelectron angular distributions (PADs) that have averaged over partial alignments of isolated molecules. The photoelectron is pulled out from a localized inner-shell molecular orbital by an X-ray photon. We show that a transient change in the atomic positions from their equilibrium will lead to a sensitive change in the alignment-averaged PADs, which can be measured and used to retrieve the former. Exploiting the experimental convenience of changing the photon polarization direction, we show that it is advantageous to use PADs obtained from multiple photon polarization directions. Lastly, amore » simple single-scattering model is proposed and benchmarked to describe the photoionization process and to do the retrieval using a multiple-parameter fitting method.« less

  6. Retrieving transient conformational molecular structure information from inner-shell photoionization of laser-aligned molecules

    PubMed Central

    Wang, Xu; Le, Anh-Thu; Yu, Chao; Lucchese, R. R.; Lin, C. D.

    2016-01-01

    We discuss a scheme to retrieve transient conformational molecular structure information using photoelectron angular distributions (PADs) that have averaged over partial alignments of isolated molecules. The photoelectron is pulled out from a localized inner-shell molecular orbital by an X-ray photon. We show that a transient change in the atomic positions from their equilibrium will lead to a sensitive change in the alignment-averaged PADs, which can be measured and used to retrieve the former. Exploiting the experimental convenience of changing the photon polarization direction, we show that it is advantageous to use PADs obtained from multiple photon polarization directions. A simple single-scattering model is proposed and benchmarked to describe the photoionization process and to do the retrieval using a multiple-parameter fitting method. PMID:27025410

  7. Excitation of the symmetry forbidden bending mode in molecular photoionization

    NASA Astrophysics Data System (ADS)

    Miller, J. Scott; Poliakoff, E. D.; Miller, Thomas F.; Natalense, Alexandra P. P.; Lucchese, Robert R.

    2001-03-01

    We present results on the energy dependence of the vibrational branching ratio for the bending mode in CO2 3σu-1 photoionization. Specifically, we determine the v+=(0,1,0)/v+=(0,0,0) intensity ratio by detecting dispersed fluorescence from the electronically excited photoions. The results exhibit large deviations over a very wide energy range, 18photoionization spectroscopies. The magnitude of these deviations display the utility of vibrationally resolved studies, and the extent over which these changes occur underscores the necessity of broad range studies to elucidate slowly varying characteristics in photoionization continua.

  8. Rotationally resolved fluorescence as a probe of molecular photoionization dynamics

    NASA Astrophysics Data System (ADS)

    Kakar, Sandeep; Choi, Heung-Cheun; Poliakoff, E. D.

    1992-11-01

    We present rotationally resolved data for the v'=0 and v'=1 levels of N2+(B 2Σu+) produced via 2σu-1 photoionization of N2. The data are obtained over a broad photon energy range (19≤hνexc≤35 eV). This is made possible by using synchrotron radiation excitation in conjunction with dispersed fluorescence detection. The results exhibit both resonant and nonresonant effects.

  9. Measuring Magnetic Fields in Photoionized Interstellar Plasmas (HII Regions)

    NASA Astrophysics Data System (ADS)

    Spangler, Steven; Costa, Allison

    2015-11-01

    Hot luminous stars photoionize the interstellar gas around them, creating plasmas with a very high ionization fraction. In astronomical terminology, these are called HII regions. They are dynamic plasmas, expanding due to overpressure with respect to the interstellar medium. We are making diagnostic measurements to determine the strength and structure of magnetic fields in these objects. This paper presents our results on the Rosette Nebula. We diagnose the magnetic field in the Rosette by measurements of Faraday rotation on lines of sight passing through the nebula. These measurements are made with the Very Large Array radio telescope of the National Radio Astronomy Observatory. We have measurements of the rotation measure for 18 lines of sight. Values of the mean, line of sight component of the magnetic field range from about 3 to 5 microGauss. We will discuss comparison of these measurements with models for modification of the interstellar magnetic field by an HII region. This work was supported by grants AST09-07911 and ATM09-56901 from the National Science Foundation.

  10. Correlation of molecular valence- and K-shell photoionization resonances with bond lengths

    NASA Technical Reports Server (NTRS)

    Sheehy, J. A.; Gil, T. J.; Winstead, C. L.; Farren, R. E.; Langhoff, P. W.

    1989-01-01

    The relationship between the interatomic distance and the positions of valence-shell and K-shell sigma(asterisk) photoionization resonances is investigated theoretically for the molecules C2, F2, N2, O2, CO, NO, C2H2, C2H4, C2H6, HCN, H2CO, N20, CO2, and C2N2. The results of molecular-orbital computations are presented in three-dimensional diagrams, which are shown to be similar to the wave functions of a particle in a cylindrical well, confirming the validity of free-electron molecular-orbital (FEMO) approximations for modeling the potential along the symmetry axis. FEMO orbital energies and resonance positions are found to be in good agreement with previous theoretical and experimental results. Also included is a Feshbach-Fano analysis of the relevance of virtual-valence orbitals to the appearance of single-channel resonances in molecular photoionization cross sections.

  11. Molecular Frame Photoemission: Probe of the Photoionization Dynamics for Molecules in the Gas Phase

    NASA Astrophysics Data System (ADS)

    Dowek, D.; Picard, Y. J.; Billaud, P.; Elkharrat, C.; Houver, J. C.

    2009-04-01

    Molecular frame photoemission is a very sensitive probe of the photoionization (PI) dynamics of molecules. This paper reports a comparative study of non-resonant and resonant photoionization of D2 induced by VUV circularly polarized synchrotron radiation at SOLEIL at the level of the molecular frame photoelectron angular distributions (MFPADs). We use the vector correlation method which combines imaging and time-of-flight resolved electron-ion coincidence techniques, and a generalized formalism for the expression of the I(χ, θe, varphie) MFPADs, where χ is the orientation of the molecular axis with respect to the light quantization axis and (θe, varphie) the electron emission direction in the molecular frame. Selected MFPADs for a molecule aligned parallel or perpendicular to linearly polarized light, or perpendicular to the propagation axis of circularly polarized light, are presented for dissociative photoionization (DPI) of D2 at two photon excitation energies, hν = 19 eV, where direct PI is the only channel opened, and hν = 32.5 eV, i.e. in the region involving resonant excitation of Q1 and Q2 doubly excited state series. We discuss in particular the properties of the circular dichroism characterizing photoemission in the molecular frame for direct and resonant PI. In the latter case, a remarkable behavior is observed which may be attributed to the interference occurring between undistinguishable autoionization decay channels.

  12. Interference in the molecular photoionization and Young's double-slit experiment

    NASA Astrophysics Data System (ADS)

    Baltenkov, A. S.; Becker, U.; Manson, S. T.; Msezane, A. Z.

    2012-02-01

    The photoabsorption by an electron bound by a two-centre potential has been investigated within the framework of the zero-range potential model. Expressions for total photoabsorption cross sections and for the photoelectron angular distributions have been derived for fixed-in-space and randomly oriented targets. The analytical formulae for gerade and ungerade molecular states have been used to analyse separately the molecular effects due to the two-centre ground state of quasi-molecule and diffraction effects that are connected with the spherical waves in the molecular continuum. It is shown that the interference of these waves significantly influences the magnitude of the cross sections near threshold but does not significantly distort the shape of the photoelectron angular distribution and it depends rather weakly on the character of the forces acting between the electron and molecular residue: Coulomb forces for neutral molecular photoionization or the short-range forces in the case of photodetachment of molecular negative ions. It is shown that despite the fact that the photoionization of diatomic molecules is reminiscent of Young's double-slit experiment, the similarity between these processes has been grossly exaggerated. This is confirmed by comparing the results of the classical interference of an electron scattered by two spatially separated centres with molecular photoelectron angular distributions.

  13. Photoionization of triatomic molecular ions {{\\rm{H}}}_{3}^{2+} by intense bichromatic circularly polarized attosecond UV laser pulses

    NASA Astrophysics Data System (ADS)

    Yuan, Kai-Jun; Lu, Huizhong; Bandrauk, André D.

    2017-06-01

    Photoionization of triatomic molecular ions has been studied for triangular and linear geometries by bichromatic circularly polarized attosecond UV laser pulses at frequencies {ω }2=2{ω }1. Simulations are performed on the single electron molecule {{{H}}}32+ by numerically solving time-dependent Schrödinger equations. We measure molecular frame photoelectron momentum distributions (MFPMDs), which show spiral electron vortex patterns as functions of the helicity of the pulse and the molecular geometry. The ionization interference effects arise from multi-pathway ionization, which give rise to the modulation of multi-center photoelectron spectra. We describe these phenomena in MFPMDs based on an ultrafast delta-function ionization model and attosecond perturbation ionization theory. Interference patterns in MFPMDs reflect the helicity and symmetry of the electric fields in the attosecond ionizing pulses.

  14. A VUV photoionization measurement and ab-initio calculation of the ionization energy of gas phase SiO2

    SciTech Connect

    Kostko, Oleg; Ahmed, Musahid; Metz, Ricardo B.

    2008-12-05

    In this work we report on the detection and vacuum-ultraviolet (VUV) photoionization of gas phase SiO2 generated in situ via laser ablation of silicon in a CO2 molecular beam. The resulting species are investigated by single photon ionization with tunable VUV synchrotron radiation and mass analyzed using reflectron mass spectrometry. Photoionization efficiency (PIE) curves are recorded for SiO and SiO2 and ionization energy estimates are revealed from such measurements. A state-to-state ionizationenergy of 12.60 (+-0.05) eV is recorded by fitting two prominent peaks in the PIE curve for the following process: 1SUM O-Si-O --> 2PRODg [O-Si-O]+. Electronic structure calculations aid in the interpretation of the photoionization process and allow for identification of the symmetric stretch of 2PRODg [O-Si-O]+ which is observed in the PIE spectrum to be 0.11 eV (890 cm-1) above the ground state of the cation and agrees with the 892 cm-1 symmetric stretch frequency calculated at the CCSD(T)/aug-cc-pVTZ level.

  15. Total molecular photoionization cross-sections by algebraic diagrammatic construction-Stieltjes-Lanczos method: Benchmark calculations

    NASA Astrophysics Data System (ADS)

    Ruberti, M.; Yun, R.; Gokhberg, K.; Kopelke, S.; Cederbaum, L. S.; Tarantelli, F.; Averbukh, V.

    2013-10-01

    In [K. Gokhberg, V. Vysotskiy, L. S. Cederbaum, L. Storchi, F. Tarantelli, and V. Averbukh, J. Chem. Phys. 130, 064104 (2009)] we introduced a new {L}2ab initio method for the calculation of total molecular photoionization cross-sections. The method is based on the ab initio description of discretized photoionized molecular states within the many-electron Green's function approach, known as algebraic diagrammatic construction (ADC), and on the application of Stieltjes-Chebyshev moment theory to Lanczos pseudospectra of the ADC electronic Hamiltonian. Here we establish the accuracy of the new technique by comparing the ADC-Lanczos-Stieltjes cross-sections in the valence ionization region to the experimental ones for a series of eight molecules of first row elements: HF, NH3, H2O, CO2, H2CO, CH4, C2H2, and C2H4. We find that the use of the second-order ADC technique [ADC(2)] that includes double electronic excitations leads to a substantial systematic improvement over the first-order method [ADC(1)] and to a good agreement with experiment for photon energies below 80 eV. The use of extended second-order ADC theory [ADC(2)x] leads to a smaller further improvement. Above 80 eV photon energy all three methods lead to significant deviations from the experimental values which we attribute to the use of Gaussian single-electron bases. Our calculations show that the ADC(2)-Lanczos-Stieltjes technique is a reliable and efficient ab initio tool for theoretical prediction of total molecular photo-ionization cross-sections in the valence region.

  16. Total molecular photoionization cross-sections by algebraic diagrammatic construction-Stieltjes-Lanczos method: benchmark calculations.

    PubMed

    Ruberti, M; Yun, R; Gokhberg, K; Kopelke, S; Cederbaum, L S; Tarantelli, F; Averbukh, V

    2013-10-14

    In [K. Gokhberg, V. Vysotskiy, L. S. Cederbaum, L. Storchi, F. Tarantelli, and V. Averbukh, J. Chem. Phys. 130, 064104 (2009)] we introduced a new L(2) ab initio method for the calculation of total molecular photoionization cross-sections. The method is based on the ab initio description of discretized photoionized molecular states within the many-electron Green's function approach, known as algebraic diagrammatic construction (ADC), and on the application of Stieltjes-Chebyshev moment theory to Lanczos pseudospectra of the ADC electronic Hamiltonian. Here we establish the accuracy of the new technique by comparing the ADC-Lanczos-Stieltjes cross-sections in the valence ionization region to the experimental ones for a series of eight molecules of first row elements: HF, NH3, H2O, CO2, H2CO, CH4, C2H2, and C2H4. We find that the use of the second-order ADC technique [ADC(2)] that includes double electronic excitations leads to a substantial systematic improvement over the first-order method [ADC(1)] and to a good agreement with experiment for photon energies below 80 eV. The use of extended second-order ADC theory [ADC(2)x] leads to a smaller further improvement. Above 80 eV photon energy all three methods lead to significant deviations from the experimental values which we attribute to the use of Gaussian single-electron bases. Our calculations show that the ADC(2)-Lanczos-Stieltjes technique is a reliable and efficient ab initio tool for theoretical prediction of total molecular photo-ionization cross-sections in the valence region.

  17. Spectral investigations of photoionized plasmas induced in atomic and molecular gases using nanosecond extreme ultraviolet (EUV) pulses

    NASA Astrophysics Data System (ADS)

    Bartnik, A.; Fiedorowicz, H.; Wachulak, P.

    2014-07-01

    In this paper, results of spectral investigations of low temperature photoionized plasmas, created by irradiation of gases with intense pulses of extreme ultraviolet (EUV) radiation from a laser-produced plasma (LPP) source, are presented. The LPP source was based on a double-stream KrXe/He gas-puff target irradiated with 4 ns/0.8 J/10 Hz Nd:YAG laser pulses. The most intense emission from the source spanned a relatively narrow spectral region λ ≈ 10-12 nm; however, spectrally integrated intensity at longer wavelengths was also significant. The EUV beam was focused on a gas stream, injected into a vacuum chamber synchronously with the EUV pulses. Irradiation of gases resulted in formation of photoionized plasmas emitting radiation in the EUV range. Radiation spectra, measured for plasmas produced in various gases, are dominated by emission lines, originating from single charged ions. Significant differences in spectral intensities and distributions between plasmas created in neon and molecular gases were observed.

  18. Spectral investigations of photoionized plasmas induced in atomic and molecular gases using nanosecond extreme ultraviolet (EUV) pulses

    SciTech Connect

    Bartnik, A.; Fiedorowicz, H.; Wachulak, P.

    2014-07-15

    In this paper, results of spectral investigations of low temperature photoionized plasmas, created by irradiation of gases with intense pulses of extreme ultraviolet (EUV) radiation from a laser-produced plasma (LPP) source, are presented. The LPP source was based on a double-stream KrXe/He gas-puff target irradiated with 4 ns/0.8 J/10 Hz Nd:YAG laser pulses. The most intense emission from the source spanned a relatively narrow spectral region λ ≈ 10–12 nm; however, spectrally integrated intensity at longer wavelengths was also significant. The EUV beam was focused on a gas stream, injected into a vacuum chamber synchronously with the EUV pulses. Irradiation of gases resulted in formation of photoionized plasmas emitting radiation in the EUV range. Radiation spectra, measured for plasmas produced in various gases, are dominated by emission lines, originating from single charged ions. Significant differences in spectral intensities and distributions between plasmas created in neon and molecular gases were observed.

  19. Molecular Structure and Dynamics Probed by Photoionization Out of Rydberg States

    NASA Astrophysics Data System (ADS)

    Rudakov, Fedor

    2017-06-01

    Probing the structure of a molecule as a chemical reaction unfolds has been a long standing goal in chemical physics. Most spectroscopic and diffraction techniques work well when the molecules are cold and thus vibrational motion is minimized. Yet, the very ability of a molecule to undergo structural changes implies that a significant amount of energy resides within the molecule. In order to probe structures of even medium sized molecules on an ultrafast time scale a technique that is sensitive to the molecular structure, yet insensitive to the vibrational motion is required. In our research we demonstrated that Rydberg electrons are remarkably sensitive to the molecular structure. Photoionization of a molecule out of Rydberg states reveals a purely electronic spectrum which is largely insensitive to vibrational motion. The talk illustrates how Rydberg electrons can serve as a probe for ultrafast structural dynamics in polyatomic molecules. The talk also demonstrates that photoionization through Rydberg states can be utilized for non-intrusive detection of polyatomic combustion intermediates in flames.

  20. Balloon-borne photoionization mass spectrometer for measurement of stratospheric gases

    NASA Technical Reports Server (NTRS)

    Aikin, A. C.; Maier, E. J. R.

    1978-01-01

    A balloon-borne photoionization mass spectrometer used to measure stratospheric trace gases is described. Ions are created with photons from high-intensity krypton discharge lamps and a quadrupole mass analyzer is employed for ion identification. Differential pumping is achieved with liquid helium cryopumping. To insure measurement of unperturbed stratospheric air, the entire system is contained in a sealed gondola and the atmospheric sample is taken some distance away during descent. The photoionization technique allows the detection of a low ionization potential constituent, such as nitric oxide, at less than a part in one billion in the presence of the major atmospheric gases and their isotopes. Operation of the mass spectrometer system was demonstrated during a daytime flight from Palestine, Texas on 26 April 1977. The sensitivity achieved and the unique selectivity afforded by this technique offer a capability for trace constituent measurement not possible with the more conventional electron impact ionization approach.

  1. Absolute single photoionization cross-section measurements of Rb2+ ions: experiment and theory

    NASA Astrophysics Data System (ADS)

    Macaluso, D. A.; Bogolub, K.; Johnson, A.; Aguilar, A.; Kilcoyne, A. L. D.; Bilodeau, R. C.; Bautista, M.; Kerlin, A. B.; Sterling, N. C.

    2016-12-01

    Absolute single photoionization cross-section measurements of Rb2+ ions were performed using synchrotron radiation and the photo-ion, merged-beams technique at the Advanced Light Source at Lawrence Berkeley National Laboratory. Measurements were made at a photon energy resolution of 13.5 ± 2.5 meV from 37.31 to 44.08 eV spanning the 2P{}3/2o ground state and 2P{}1/2o metastable state ionization thresholds. Multiple autoionizing resonance series arising from each initial state are identified using quantum defect theory. The measurements are compared to Breit-Pauli R-matrix calculations with excellent agreement between theory and experiment.

  2. A hybridGaussian-discrete variable representation approach to molecular continuum processes II: application to photoionization of diatomic Li2+

    SciTech Connect

    Rescigno, Thomas N; Yip, Frank L.; McCurdy, C. William; Rescigno, Thomas N.

    2008-08-01

    We describe an approach for studying molecular photoionization with a hybrid basis that combines the functionality of analytic basis sets to represent electronic coordinates near the nuclei of a molecule with numerically-defined grid-based functions. We discuss the evaluation of the various classes of two-electron integrals that occur in a hybrid basis consisting of Gaussian type orbitals (GTOs) and discrete variable representation (DVR) functions. This combined basis is applied to calculate single photoionization cross sections for molecular Li_2+, which has a large equilibrium bond distance (R=5.86a_0). The highly non-spherical nature of Li_2+ molecules causes higher angular momentum components to contribute significantly to the cross section even at low photoelectron energies, resulting in angular distributions that appear to be f-wave dominated near the photoionization threshold. At higher energies, where the de Broglie wavelength of the photoelectron becomes comparable with the bond distance, interference effects appear in the photoionization cross section. These interference phenomena appear at much lower energies than would be expected for diatomic targets with shorter internuclear separations.

  3. High-Resolution Measurements of Photoionization of Ions Using Synchrotron Radiation

    SciTech Connect

    Aguilar, A.; Covington, A.M.; Emmons, E.D.; Gharaibeh, M.F.; Phaneuf, R.A.; Alvarez, I.; Cisneros, C.; Hinojosa, G.; Dominguez, I.; Ackerman, G.; Bozek, J.D.; Canton, S.; Rude, B.; Sant'Anna, M.M.; Schlachter, A. S.; Folkmann, F.

    2003-08-26

    Measurement of absolute cross sections for photoionization of ions has become feasible by merging a well-collimated ion beam with a monochromatic beam of synchrotron radiation. An electron cyclotron resonance (ECR) ion source permits such measurements to be extended to multiply charged ions, and makes possible systematic studies along isoelectronic sequences. The evolution of atomic spectra along such sequences is commonly studied theoretically, but the predictive ability of the theoretical methods remains largely untested. Absolute cross-section measurements are presented for the first three ionic members of the isoelectronic sequence of nitrogen (O+, F2+ and Ne3+)

  4. Dynamics of photoionization from molecular electronic wavepacket states in intense pulse laser fields: A nonadiabatic electron wavepacket study

    NASA Astrophysics Data System (ADS)

    Matsuoka, Takahide; Takatsuka, Kazuo

    2017-04-01

    A theory for dynamics of molecular photoionization from nonadiabatic electron wavepackets driven by intense pulse lasers is proposed. Time evolution of photoelectron distribution is evaluated in terms of out-going electron flux (current of the probability density of electrons) that has kinetic energy high enough to recede from the molecular system. The relevant electron flux is in turn evaluated with the complex-valued electronic wavefunctions that are time evolved in nonadiabatic electron wavepacket dynamics in laser fields. To uniquely rebuild such wavefunctions with its electronic population being lost by ionization, we adopt the complex-valued natural orbitals emerging from the electron density as building blocks of the total wavefunction. The method has been implemented into a quantum chemistry code, which is based on configuration state mixing for polyatomic molecules. Some of the practical aspects needed for its application will be presented. As a first illustrative example, we show the results of hydrogen molecule and its isotope substitutes (HD and DD), which are photoionized by a two-cycle pulse laser. Photon emission spectrum associated with above threshold ionization is also shown. Another example is taken from photoionization dynamics from an excited state of a water molecule. Qualitatively significant effects of nonadiabatic interaction on the photoelectron spectrum are demonstrated.

  5. CaH Rydberg series, oscillator strengths and photoionization cross sections from Molecular Quantum Defect and Dyson Orbital theories

    NASA Astrophysics Data System (ADS)

    Velasco, A. M.; Lavín, C.; Díaz-Tinoco, Manuel; Ortiz, J. V.

    2017-01-01

    In this work, electron-propagator methods are applied to the calculation of the ionization potential and vertical excitation energies for several Rydberg series of the CaH molecule. The present calculations cover more highly excited states than those previously reported. In particular, excitation energies for ns (n>5), np (n>5), nd (n>4) and nf Rydberg states are given. Oscillator strengths for electronic transitions involving Rydberg states of CaH, as well as photoionization cross sections for Rydberg channels, also have been determined by using the Molecular Quantum Defect Orbital approach. Good agreement has been found with the scarce comparative data that are available for oscillator strengths. To our knowledge, predictions of photoionization cross sections from the outermost orbital of CaH are made here for the first time. A Cooper minimum and mixed atomic orbital character in some of the Dyson orbitals are among the novel features of these present calculations.

  6. Photoionization and photofragmentation of the C60+ molecular ion

    SciTech Connect

    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 C$+\\atop{60}$ 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 C$+\\atop{60}$ 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. Lastly, this comparison and an accounting of oscillator strengths indicate that with the exception of C$+\\atop{58}$, 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.

  7. Spectroscopy of defects in HPHT and CVD diamond by ESR and pulsed photo-ionization measurements

    NASA Astrophysics Data System (ADS)

    Gaubas, E.; Ceponis, T.; Meskauskaite, D.; Grigonis, R.; Sirutkaitis, V.

    2016-01-01

    Synthetic diamond is one of the most promising wide band-gap materials for fabrication of solar-blind photo-sensors and radiation tolerant particle detectors. However, defects introduced during crystal growth and processing, causing carrier trapping and recombination, limit the functional characteristics of devices made of this material. In order to reveal the predominant defects, pulsed photo-ionization (PPI), Fourier transform infrared (FTIR) and electron spin resonance (ESR) spectroscopic measurements have been performed on diamond samples grown by chemical vapor deposition (CVD) and high pressure-high temperature (HPHT) methods. Measured photo-activation energies have been assigned to point defects associated with nitrogen and nickel impurities as well as to their complexes involving vacancies.

  8. Quantitative energy extraction measurements in a photoionization-stabilized self-sustained XeF laser

    NASA Technical Reports Server (NTRS)

    Lee, C. M.; Hasson, V.; Rowley, P. D.; Exberger, R.

    1979-01-01

    Detailed time-correlated gain, fluorescence, and laser energy measurements were used to obtain quantitative data on energy extraction efficiencies for a photoionization-stabilized self-sustained XeF laser. A current pulse of 25 ns full width at half-maximum produced an 80-cu-cm XeF plasma in NF3:Xe:He gas mixtures with a maximum output energy of 80 mJ. The results show that the maximum small-signal gain and the maximum specific output energy is proportional to the NF3 content of the gas mixture. This suggests that there is an optimum fractional utilization of the NF3 molecules in the discharge. Under high-gain conditions, 30-40% of the energy stored in XeF(asterisk) can be extracted in a gain-switched pulse. The output energy represents less than 1% of the input energy.

  9. Molecular photoionization as a probe of vibrational-rotational-electronic correlations

    NASA Astrophysics Data System (ADS)

    Rao, R. M.; Poliakoff, E. D.; Wang, Kwanghsi; McKoy, V.

    1996-06-01

    We determine the rotationally state-resolved 2σu-1 photoionization of N2 into alternative vibrational channels as a function of energy over a 200 eV range. Experiment and theory reveal that Cooper minima highlight the coupling between electronic, vibrational, and rotational degrees of freedom over this very wide range.

  10. High efficiency photoionization detector

    DOEpatents

    Anderson, D.F.

    1984-01-31

    A high efficiency photoionization detector is described using tetraaminoethylenes in a gaseous state having a low ionization potential and a relative photoionization cross section which closely matches the emission spectrum of xenon gas. Imaging proportional counters are also disclosed using the novel photoionization detector of the invention. The compound of greatest interest is TMAE which comprises tetrakis(dimethylamino)ethylene which has a measured ionization potential of 5.36 [+-] 0.02 eV, and a vapor pressure of 0.35 torr at 20 C. 6 figs.

  11. High efficiency photoionization detector

    DOEpatents

    Anderson, David F.

    1984-01-01

    A high efficiency photoionization detector using tetraaminoethylenes in a gaseous state having a low ionization potential and a relative photoionization cross section which closely matches the emission spectrum of xenon gas. Imaging proportional counters are also disclosed using the novel photoionization detector of the invention. The compound of greatest interest is TMAE which comprises tetrakis(dimethylamino)ethylene which has a measured ionization potential of 5.36.+-.0.02 eV, and a vapor pressure of 0.35 torr at 20.degree. C.

  12. Ultrafast molecular photoionization by two-color orthogonally polarized ultraviolet laser pulses: Effects of relative pulse phases

    NASA Astrophysics Data System (ADS)

    Yuan, Kai-Jun; Chelkowski, Szczepan; Bandrauk, André D.

    2017-09-01

    We present molecular photoionization by two-color 2ω1 =ω2 orthogonally polarized ultraviolet laser pulses. Simulations are performed on aligned H+ by numerically solving time-dependent Schrödinger equations. Two ionization processes with one ω2 photon interfering with two ω1 photon absorption are studied at different molecular alignments. Molecular frame photoelectron momentum and angular distributions exhibit asymmetries which are functions of the relative pulse phase. For resonant excitation processes by the ω1 pulse, symmetric distributions are obtained. An attosecond ionization model is adopted to describe the ultrafast ionization dynamics. The dependence of the ionization asymmetry on the molecular alignment allows to further monitor interference effects on orbital symmetry.

  13. Photoionization of oxidized metal clusters

    SciTech Connect

    Dao, P.D.; Peterson, K.I.; Castleman, A.W. Jr.

    1984-01-01

    Oxidized metal clusters (Na/sub x/O and K/sub x/O for 2< or =x< or =4) were formed in a gas phase reaction between metal clusters and an oxidizing gas using a double expansion technique. Their appearance potentials were measured using a molecular beam-photoionization mass spectrometer system. These first photoionization data for oxidized clusters provide information on trends of ionization potentials as a function of the degree of aggregation. The ionization potentials do not differ greatly from the analogous metallic species, but in the case of the sodium tetramer the value does fall below that of the bare metal cluster. This finding is in accord with what has been observed as an influence of impurities on the work function of the bulk sodium. The results are also of interest concerning questions of octet rule violations and hypervalency.

  14. Relative Photoionization Cross Sections of Super-Atom Molecular Orbitals (SAMOs) in C60.

    PubMed

    Bohl, Elvira; Sokół, Katarzyna P; Mignolet, Benoit; Thompson, James O F; Johansson, J Olof; Remacle, Francoise; Campbell, Eleanor E B

    2015-11-25

    The electronic structure and photoinduced dynamics of fullerenes, especially C60, is of great interest because these molecules are model systems for more complex molecules and nanomaterials. In this work we have used Rydberg Fingerprint Spectroscopy to determine the relative ionization intensities from excited SAMO (Rydberg-like) states in C60 as a function of laser wavelength. The relative ionization intensities are then compared to the ratio of the photoionization widths of the Rydberg-like states, computed in time-dependent density functional theory (TD-DFT). The agreement is remarkably good when the same photon order is required to energetically access the excited states. This illustrates the predictive potential of quantum chemistry for studying photoionization of large, complex molecules as well as confirming the assumption that is often made concerning the multiphoton excitation and rapid energy redistribution in the fullerenes.

  15. Using vibrational branching ratios to probe initial and final state effects in molecular photoionization

    NASA Astrophysics Data System (ADS)

    Lucchese, Robert R.; Bozek, John D.; Das, Aloke; Poliakoff, E. D.

    2009-11-01

    Recent computed and experimental results for ICN, BF3 and C6F6 will be presented. In ICN we consider the ionization leading to the X2 Π1/2,3/2 states of ICN+. We show how the geometry dependence of the initial state orbital can be studied using vibrational branching ratios. In C6F6, we consider the excitation of the effects of two prominent shape resonances on the symmetric stretching modes in the photoionization leading to the C 3B2u state of the ion. In BF3, the excitation of both the symmetric stretching and the degenerate asymmetric stretching modes are considered in the photoionization leading to the E2A1' state of the ion.

  16. On the correlation between photoelectron energy and bending excitation in molecular photoionization

    NASA Astrophysics Data System (ADS)

    Miller, J. Scott; Poliakoff, E. D.

    2000-07-01

    We report on excitation of the bending vibration following 3σu-1 photoionization of CO2. Dispersed fluorescence is used to determine the v+=(0,1,0)/v+=(0,0,0) ratio over the range 18⩽hνexc⩽190 eV. The results demonstrate that the bending excitation varies over this wide range, and is influenced by the photoelectron.

  17. Classical two-split interference effects in double photoionization of molecular hydrogen at high energies

    SciTech Connect

    Horner, Daniel A; Miyabe, S; Rescigno, T N; Mccurdy, C W; Morales, F; Martin, F

    2009-01-01

    The authors report a thorough theoretical study of one photon double ionization of H{sub 2}. They suggest that interference effects reported in one photon ionization will be reproducible in the case of double ionization when one of the photons carriers most of the available energy and the other electron is not observed. These calculations reproduce recent double photoionization experiments of H{sub 2}.

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

    NASA Astrophysics Data System (ADS)

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

    2016-03-01

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

  19. A multireference configuration interaction study of CuB and CuAl molecular constants and photoionization spectra.

    PubMed

    Ferrão, Luiz F A; Spada, Rene F K; Roberto-Neto, Orlando; Machado, Francisco B C

    2013-09-28

    Accurate potential energy curves and molecular constants for the low-lying electronic states of CuX(y) (X = B, Al; y = 0, +1) were investigated using the complete active space self-consistent field/multireference configuration interaction (MRCI) methodology with aug-cc-pV5Z basis set. The photoionization spectra of CuX were computed, showing electron detachment in the region of far ultraviolet. The results complement the previous theoretical characterizations and the few experimental studies. A comparative analysis was carried out concerning the different choices of reference configuration state functions in the MRCI calculations with and without the contribution of scalar relativistic effects. The results obtained with a small reference set adequately constructed are competitive to those using a much larger number of configuration state functions, and also the scalar relativistic effects improve significantly the molecular constants in this kind of system containing a 3d metal atom.

  20. Measurements of fluorescence and Coster-Kronig yields for 66Dy using synchrotron radiation induced selective photoionization method

    NASA Astrophysics Data System (ADS)

    Kaur, Rajnish; Kumar, Anil; Czyzycki, M.; Migliori, A.; Karydas, A. G.; Puri, Sanjiv

    2017-09-01

    The L shell fluorescence (ω1, ω2, ω3) and Coster-Kronig (f12, f13, f23) yields for 66Dy have been deduced from the Li (i = 1-3) sub-shell X-ray intensities measured at different incident photon energies across its Li absorption edge energies. Three sets of photoionization cross sections used for determination of these yields include two sets of theoretical values based on the non-relativistic Hartree-Fock-Slater model and the self-consistent Dirac-Hartree-Fock model, and the third one is that deduced from independently measured mass attenuation coefficients of 66Dy. The present experimental fluorescence and Coster-Kronig yields deduced using the self-consistent Dirac-Hartree-Fock model based photoionization cross sections have been found to be in good agreement with the semi-empirical values tabulated by Krause [1] and the Dirac-Hartree-Slater model based values.

  1. Triply Differential Studies of Atomic and Molecular Photoionization Using Synchrotron Radiation.

    DTIC Science & Technology

    1981-07-06

    1980). 9. E. D. Poliakoff , P. M. Dehmer, J. L. Dehmer, and R. L. Stockbauer, "The Photoelectron Spectrum of Xe 3 by the Photoclectron-Photoion...4. E. D. Poliakoff , J. L. Dehmer, A. C. Parr, D. Dill, K. H. Jackson, an, R. N. Zare, "Polarized Fluorescence Excta:b,, Spectroscopy of N2 , " ibid...p. 11-25. 5. J. L. Dehmer, A. C. Parr, J. B. West, K. Codling, D. L. Ederer, B. E. Cole, E. D. Poliakoff , and R. Stockbauer, "Ef,, cts of Shape

  2. Measurement of relative L X-ray intensity ratio following radioactive decay and photoionization

    NASA Astrophysics Data System (ADS)

    Yalçın, P.; Porikli, S.; Kurucu, Y.; Şahin, Y.

    2008-05-01

    The measurements of the L X-ray intensity ratio I (Lα) / I (Lβ), I (Lα) / I (Lγ), I (Lα) / I (Lι), I (Lβ) / I (Lγ) and I (Lι) / I (Lγ) for elements Dy, Ho, Yb, W, Hg, Tl and Pb were experimentally determined both by photon excitation, in which 59.5 keV γ-rays from a filtered radioisotope 241Am was used, and by the radioactive decay of 160Tb, 160Er, 173Lu, 182Re, 201Tl, 203Pb and 207Bi. L X-rays emitted by samples were counted by a Si(Li) detector with resolution 160 eV at 5.9 keV. Obtained values were compared with the calculated theoretical values. Theoretical values of the I (Lα / Lβ), I (Lα / Lγ), I (Lα / Lι), I (Lβ / Lγ) and I (Lι / Lγ) intensity ratios were calculated using theoretically tabulated values of subshell photoionization cross-section, fluorescence yield, fractional X-ray emission rates, Coster-Kronig transition probabilities. It was observed that present values agree with previous theoretical and other available experimental results.

  3. Non-selective photoionization for isotope ratio measurements by time of flight mass spectrometry with laser ablation

    NASA Astrophysics Data System (ADS)

    Vors, E.; Semerok, A.; Wagner, J.-F.; Fomichev, S. V.

    2000-12-01

    Isotope ratio measurements of metallic uranium samples were carried out by linear TOF mass spectrometry in combination with laser ablation. To eliminate the problems resulting from laser plasma ion energy and spatial dispersions, the uranium atoms were post-ionized by the third harmonic of a Nd-YAG laser. Experimental and theoretical results of the LA-TOF performance and non-selective photoionization of uranium atoms produced by laser ablation are presented.

  4. Laboratory and field measurements of organic aerosols with the photoionization aerosol mass spectrometer

    NASA Astrophysics Data System (ADS)

    Dreyfus, Matthew A.

    Analytical methods developed to sample and characterize ambient organic aerosols often face the trade-off between long sampling times and the loss of detailed information regarding specific chemical species present. The soft, universal ionization scheme of the Photoionization Aerosol Mass Spectrometer (PIAMS) allows for identification of various chemical compounds by a signature ion, often the molecular ion. The goal of this thesis work is to apply PIAMS to both laboratory and field experiments to answer questions regarding the formation, composition, and behavior of organic aerosols. To achieve this goal, a variety of hardware and software upgrades were administered to PIAMS to optimize the instrument. Data collection and processing software were either refined or built from the ground up to simplify difficult or monotonous tasks. Additional components were added to PIAMS with the intent to automate the instrument, enhance the results, and make the instrument more rugged and user-friendly. These changes, combined with the application of an external particle concentration system (mini-Versatile Aerosol Concentration Enrichment System, m-VACES), allowed PIAMS to be suitable for field measurements of organic aerosols. Two such field campaigns were completed, both at the State of Delaware Air Quality Monitoring Site in Wilmington, Delaware: a one week period in June, 2006, and an 18 day period in October and November of 2007. A sampling method developed was capable of collecting sufficient ambient organic aerosol and analyzing it with a time resolution of 3.5 minutes. Because of this method, short term concentration changes of individual species can be tracked. Combined with meteorological data, the behavior of these species can be analyzed as a function of time or wind direction. Many compounds are found at enhanced levels during the evening/night-time hours; potentially due to the combined effects of temperature inversion, and fresh emissions in a cooler environment

  5. Critical Assessment of Photoionization Efficiency Measurements for Characterization of Soot-Precursor Species

    DOE PAGES

    Johansson, K. Olof; Z?dor, Judit; Elvati, Paolo; ...

    2017-05-18

    We present a critical evaluation of photoionization efficiency (PIE) measurements coupled with aerosol mass spectrometry for the identification of condensed soot-precursor species extracted from a premixed atmospheric-pressure ethylene/oxygen/nitrogen flame. Definitive identification of isomers by any means is complicated by the large number of potential isomers at masses likely to comprise particles at flame temperatures. This problem is compounded using PIE measurements by the similarity in ionization energies and PIE-curve shapes among many of these isomers. Nevertheless, PIE analysis can provide important chemical information. For example, our PIE curves show that neither pyrene nor fluoranthene alone can describe the signal frommore » C16H10 isomers and that coronene alone cannot describe the PIE signal from C24H12 species. A linear combination of the reference PIE curves for pyrene and fluoranthene yields good agreement with flame-PIE curves measured at 202 u, which is consistent with pyrene and fluoranthene being the two major C16H10 isomers in the flame samples, but does not provide definite proof. The suggested ratio between fluoranthene and pyrene depends on the sampling conditions. We calculated the values of the adiabatic-ionization energy (AIE) of 24 C16H10 isomers. Despite the small number of isomers considered, the calculations show that the differences in AIEs between several of the isomers can be smaller than the average thermal energy at room temperature. The calculations also show that PIE analysis can sometimes be used to separate hydrocarbon species into those that contain mainly aromatic rings and those that contain significant aliphatic content for species sizes investigated in this study. Our calculations suggest an inverse relationship between AIE and the number of aromatic rings. We have demonstrated that further characterization of precursors can be facilitated by measurements that test species volatility.« less

  6. Molecular beam photoionization study of HgBr/sub 2/ and HgI/sub 2/

    SciTech Connect

    Linn, S.H.; Tzeng, W.; Brom, J.M. Jr.; Ng, C.Y.

    1983-01-01

    Photoionization efficiency (PIE) data for HgBr/sub 2//sup +/ and HgI/sub 2//sup +/ and their fragment ions have been obtained in the region 600--1350 A using an oven-type supersonic beam source. The ionization energies (IE) for the X /sup 2/Pi/sub 3/2g/ states of HgBr/sub 2//sup +/ and HgI/sub 2//sup +/ were determined to be 10.560 +- 0.003 and 9.5088 +- 0.0022 eV, respectively. The analyses of the Rydberg series converging to the /sup 2/Pi/sub 1/2g/ states of HgBr/sub 2//sup +/ and HgI/sub 2//sup +/ yield a value of 10.8846 +- 0.0012 eV for the IE of the /sup 2/Pi/sub 1/2g/ state of HgBr/sub 2//sup +/ and 10.1953 +- 0.0025 eV for that of HgI/sub 2//sup +/. The major fragment ions from HgBr/sub 2/ were identified to be HgBr/sup +/, Hg/sup +/, Br/sub 2//sup +/, and Br/sup +/ and those from HgI/sub 2/ were found to be HgI/sup +/, I/sub 2//sup +/, and I/sup +/. The measured appearance energies for HgBr/sup +/ and HgI/sup +/ allow the calculation of the bond dissociation energies for HgBr/sup +/ and HgI/sup +/ to be 55 +- 2 and 59 +- 1 kcal/mol, respectively. Similar to the observation in the PIE curves for HgCl/sub 2//sup +/ and its fragment ions, the PIE spectra for HgBr/sub 2//sup +/, HgI/sub 2//sup +/, and their fragment ions are dominated by autoionization structures exhibiting asymmetric Beutler--Fano line profiles. The comparison of the PIE curves of HgCl/sub 2//sup +/, HgBr/sub 2//sup +/, HgI/sub 2//sup +/, and Hg/sup +/ from Hg confirms the previous conclusion that these autoionizing Rydberg series can be assigned to transitions((5d)/sup 10/sigma/sub g//sup 2/sigma/sub u//sup 2/..pi../sub u//sup 4/..pi../sub g//sup 4/) ..-->.. ((5d)/sup 9/sigma/sub g//sup 2/sigma/sub u//sup 2/..pi../sub u//sup 4/..pi../sub g//sup 4/ /sup 2/D/sub plus-or-minus5/2/)np and ((5d)/sup 10/sigma/sub g//sup 2/sigma/sub u//sup 2/..pi../sub u//sup 4/..pi../sub g//sup 4/) ..-->.. ((5d)/sup 9/sigma/sub g//sup 2/sigma/sub u//sup 2/..pi../sub u//sup 4/..pi../sub g//sup 4/ /sup 2/D/sub plus

  7. Non-adiabatic molecular dynamics investigation of photoionization state formation and lifetime in Mn²⁺-doped ZnO quantum dots.

    PubMed

    Fischer, Sean A; Lingerfelt, David B; May, Joseph W; Li, Xiaosong

    2014-09-07

    The unique electronic structure of Mn(2+)-doped ZnO quantum dots gives rise to photoionization states that can be used to manipulate the magnetic state of the material and to generate zero-reabsorption luminescence. Fast formation and long non-radiative decay of this photoionization state is a necessary requirement for these important applications. In this work, surface hopping based non-adiabatic molecular dynamics are used to demonstrate the fast formation of a metal-to-ligand charge transfer state in a Mn(2+)-doped ZnO quantum dot. The formation occurs on an ultrafast timescale and is aided by the large density of states and significant mixing of the dopant Mn(2+) 3dt2 levels with the valence-band levels of the ZnO lattice. The non-radiative lifetime of the photoionization states is also investigated.

  8. State-resolved molecular photoionization dynamics of polyatomic systems: Effects of non-linear changes in molecular geometry

    NASA Astrophysics Data System (ADS)

    Miller, James Scott

    An important topic in the absorption of vacuum ultraviolet photons by molecules is the correlation between electronic and nuclear degrees of freedom during photoionization. However, no previous investigations have probed the correlation between bending excitation and photoejection dynamics over a wide spectral range. We present the first such studies by reporting the influence of bending excitation following CO2 3σu -1 and N2O 7σ-1 photoionization over the photon energy range (15 eV < hvexc < 200 eV). Using dispersed fluorescence spectroscopy in conjunction with synchrotron radiation, we determine the vibrational branching ratio v+ = (0,1,0)( 0,0,0) for the CO2+ (B 2Σu+) and N2O+ (A 2Σ+) electronic states. The relative rate of production of the υ2 = 1 upper vibrational state varies over a broad ionization energy range, and in ways that are largely unanticipated. These branching ratios exhibit a strong thermal dependence, and we are able to separate out effects due to hot-band excitation from those that are due to vibronic coupling. The data indicate that the continuum electron is responsible for the observed energy dependence in CO2 3σ u-1 photoionization. This is a previously unobserved result. Additional studies examine the influence of simultaneous excitation in the bending and symmetric stretching modes in N2O+ [A 2Σ+, v + = (1,1,0)] to determine the effect of changing the energy separation of vibronically coupled potential surfaces. Finally, the CF4 + [D 2A1, v+ = (1,0,0,0)/(0,0,0,0)] branching ratio is studied, which provides the first experimental observation of a predicted low-energy shape resonance in this photoionization pathway.

  9. Photoionization of the Buckminsterfullerene Cation.

    PubMed

    Douix, Suzie; Duflot, Denis; Cubaynes, Denis; Bizau, Jean-Marc; Giuliani, Alexandre

    2017-01-05

    Photoionization of a buckminsterfullerene ion is investigated using an ion trap and a merged beam setup coupled to synchrotron radiation beamlines and compared to theoretical calculations. Absolute measurements derived from the ion trap experiment allow discrepancies concerning the photoionization cross section of C60(+) to be solved.

  10. Comparison of measured and theoretical inverse bremsstrahlung and photoionization absorption of infrared radiation in a H-He plasma.

    NASA Technical Reports Server (NTRS)

    Billman, K. W.; Stallcop, J. R.; Rowley, P. D.; Presley, L. L.

    1972-01-01

    The absorption coefficients of 1.15- and 3.39-micrometer radiation for a homogeneous H-He plasma have been measured in a temperature and electron density range where the major absorption mechanisms are electron-ion inverse bremsstrahlung and neutral-atom photoionization. Measurements were made behind both the incident and reflected shock waves in a driven tube by recording the laser intensity transmitted along the tube diameter as a function of time. The measured values compare well with those obtained from theoretical calculations for a gas in thermodynamic equilibrium.

  11. Ultrafast Molecular Photodissociation Dynamics Studied by Femtosecond Photoelectron-Photoion Coincidence Spectroscopy

    NASA Astrophysics Data System (ADS)

    Thaler, Bernhard; Heim, Pascal; Ernst, Wolfgang E.; Koch, Markus

    2017-06-01

    To completely characterize photodissociation mechanisms with time-resolved spectroscopy, it is essential to obtain unequivocal experimental information about the fragmentation dynamics induced by the laser pulse. We apply time-resolved photoelectron-photoion coincidence (PEPICO) detection in combination with different excitation schemes to obtain a mechanistic picture of the fragmentation process. For gas phase acetone molecules excited to high lying Rydberg states we are able to disentangle different ionization channels and investigate the fragmentation behavior of each channel separately. In particular, the high differentiability of PEPICO allows to distinguish channels where fragmentation proceeds after ionization from channels with fragmentation in the neutral. We show that excited Rydberg state population undergoes internal conversion due to coupling to valence states, which takes place within (150 ± 30) fs. The corresponding non-adiabatic, ultrafast relaxation dynamics to lower lying states causes conversion of electronic to vibrational energy and is found to play a crucial role in the fragmentation process (see figure 1). By studying the influence of photon energy, pulse duration, chirp and intensity of the laser pulses, we are able to determine the energy-threshold that is required for fragmentation, as well as corresponding fragmentation ratios. Surprisingly, for excitation with pulses possessing a strong negative chirp we observe significantly reduced fragmentation, indicating different internal conversion pathways and the associated intramolecular vibrational redistribution.

  12. Photoionization of FE3+ Ions

    SciTech Connect

    Ovchinnikov, O.; Schlachter, F.

    2003-01-01

    Photoionization of Fe3+ ions was studied for the first time using synchrotron radiation from the Advanced Light Source (ALS) and the merged-beams technique. Fe3+ ions were successfully produced using ferrocene in an electron cyclotron resonance ion source (ECR). The measured yield of Fe4+ photoions as a function of photon energy revealed the presence of resonances that correspond to excitation of autoionizing states. These resonances are superimposed upon the photoion yield produced by direct photoionization, which is a smooth, slowly decreasing function of energy. The spectra for the photoionization of Fe3+ will be analyzed and compared with theory. The data collected will also serve to test models for the propagation of light through ionized matter.

  13. High-resolution absorption spectroscopy of photoionized silicon plasma, a step toward measuring the efficiency of Resonant Auger Destruction

    NASA Astrophysics Data System (ADS)

    Loisel, Guillaume; Bailey, James; Hansen, Stephanie; Nagayama, Taisuke; Rochau, Gregory; Liedhal, Duane; Mancini, Roberto

    2013-10-01

    A remarkable opportunity to observe matter in a regime where the effects of General Relativity are significant has arisen through measurements of strongly red-shifted iron x-ray lines emitted from black hole accretion disks. A major uncertainty in the spectral formation models is the efficiency of Resonant Auger Destruction (RAD), in which fluorescent K α photons are resonantly absorbed by neighbor ions. The absorbing ion preferentially decays by Auger ionization, thus reducing the emerging K α intensity. If K α lines from L-shell ions are not observed in iron spectral emission, why are such lines observed from silicon plasma surrounding other accretion powered objects? To help answer this question, we are investigating photoionized silicon plasmas produced using intense x-rays from the Z facility. The incident spectral irradiance is determined with time-resolved absolute power measurements, multiple monochromatic gated images, and a 3-D view factor model. The charge state distribution, electron temperature, and electron density are determined using space-resolved backlit absorption spectroscopy. The measurements constrain photoionized plasma models and set the stage for future emission spectroscopy directly investigating the RAD process. Sandia is a multi-program laboratory operated by Sandia Corporation, a Lockheed Martin Company, for the United States Department of Energy under contract DE-AC04-94AL85000.

  14. Gadolinium photoionization process

    DOEpatents

    Paisner, Jeffrey A.; Comaskey, Brian J.; Haynam, Christopher A.; Eggert, Jon H.

    1993-01-01

    A method is provided for selective photoionization of the odd-numbered atomic mass gadolinium isotopes 155 and 157. The selective photoionization is accomplished by circular or linear parallel polarized laser beam energy effecting a three-step photoionization pathway.

  15. Gadolinium photoionization process

    DOEpatents

    Paisner, J.A.; Comaskey, B.J.; Haynam, C.A.; Eggert, J.H.

    1993-04-13

    A method is provided for selective photoionization of the odd-numbered atomic mass gadolinium isotopes 155 and 157. The selective photoionization is accomplished by circular or linear parallel polarized laser beam energy effecting a three-step photoionization pathway.

  16. Absolute measurement of the photoionization cross section of atomic hydrogen with a shock tube for the extreme ultraviolet. [for astrophysical applications

    NASA Technical Reports Server (NTRS)

    Palenius, H. P.; Kohl, J. L.; Parkinson, W. H.

    1976-01-01

    The paper reports an experiment which is part of a program to measure the absolute values of the atomic photoionization cross sections of astrophysically abundant elements, particularly in stars and planetary atmospheres. An aerodynamic pressure-driven shock tube constructed from stainless steel with a quadratic cross section was used to measure the photoionization cross section of H I at 19 wavelength points from 910 to 609 A with experimental uncertainties between 7 and 20%. The shock tube was used to produce fully dissociated hydrogen and neon mixtures for the photoabsorption measurements.

  17. Photoionization Dynamics of Small Molecules

    SciTech Connect

    Dehmer, Joseph L.; Dill, Dan; Parr, Albert C.

    1985-01-01

    The last decade has witnessed remarkable progress in characterizing dynamical aspects of the molecular photoionization process. The general challenge is to gain physical insight into those processes occuring during photo excitation and eventual escape of the photoelectron through the anisotropic molecular field, in terms of various observables such as photoionization cross-sections and branching ratios, photoelectron angular distributions and even newer probes mentioned below. Much of the progress in this field has mirrored earlier work in atomic photoionization dynamics where many key ideas were developed (e.g., channel interaction, quantum defect analysis, potential barrier phenomena and experimental techniques). However, additional concepts and techniques were required to deal with the strictly molecular aspects of the problem, particularly the anisotropy of the multicenter molecular field and the interaction among rovibronic modes.

  18. High-efficiency photoionization detector

    SciTech Connect

    Anderson, D.F.

    1981-05-12

    A high efficiency photoionization detector using tetraaminoethylenes in a gaseous state having a low ionization potential and a relative photoionization cross section which closely matches the emission spectrum of xenon gas. Imaging proportional counters are also disclosed using the novel photoionization detector of the invention. The compound of greatest interest is TMAE which comprises tetrakis(dimethylamino)ethylene which has a measured ionization potential of 5.36 +- 0.02 eV, and a vapor pressure of 0.35 torr at 20/sup 0/C.

  19. Molecular similarity measures.

    PubMed

    Maggiora, Gerald M; Shanmugasundaram, Veerabahu

    2011-01-01

    Molecular similarity is a pervasive concept in chemistry. It is essential to many aspects of chemical reasoning and analysis and is perhaps the fundamental assumption underlying medicinal chemistry. Dissimilarity, the complement of similarity, also plays a major role in a growing number of applications of molecular diversity in combinatorial chemistry, high-throughput screening, and related fields. How molecular information is represented, called the representation problem, is important to the type of molecular similarity analysis (MSA) that can be carried out in any given situation. In this work, four types of mathematical structure are used to represent molecular information: sets, graphs, vectors, and functions. Molecular similarity is a pairwise relationship that induces structure into sets of molecules, giving rise to the concept of chemical space. Although all three concepts - molecular similarity, molecular representation, and chemical space - are treated in this chapter, the emphasis is on molecular similarity measures. Similarity measures, also called similarity coefficients or indices, are functions that map pairs of compatible molecular representations that are of the same mathematical form into real numbers usually, but not always, lying on the unit interval. This chapter presents a somewhat pedagogical discussion of many types of molecular similarity measures, their strengths and limitations, and their relationship to one another. An expanded account of the material on chemical spaces presented in the first edition of this book is also provided. It includes a discussion of the topography of activity landscapes and the role that activity cliffs in these landscapes play in structure-activity studies.

  20. Molecular similarity measures.

    PubMed

    Maggiora, Gerald M; Shanmugasundaram, Veerabahu

    2004-01-01

    Molecular similarity is a pervasive concept in chemistry. It is essential to many aspects of chemical reasoning and analysis and is perhaps the fundamental assumption underlying medicinal chemistry. Dissimilarity, the complement of similarity, also plays a major role in a growing number of applications of molecular diversity in combinatorial chemistry, high-throughput screening, and related fields. How molecular information is represented, called the representation problem, is important to the type of molecular similarity analysis (MSA) that can be carried out in any given situation. In this work, four types of mathematical structure are used to represent molecular information: sets, graphs, vectors, and functions. Molecular similarity is a pairwise relationship that induces structure into sets of molecules, giving rise to the concept of a chemistry space. Although all three concepts molecular similarity, molecular representation, and chemistry space are treated in this chapter, the emphasis is on molecular similarity measures. Similarity measures, also called similarity coefficients or indices, are functions that map pairs of compatible molecular representations, that is, representations of the same mathematical form, into real numbers usually, but not always, lying on the unit interval. This chapter presents a somewhat pedagogical discussion of many types of molecular similarity measures, their strengths and limitations, and their relationship to one another.

  1. Dissociative and double photoionization of CO2 from threshold to 90 A

    NASA Technical Reports Server (NTRS)

    Masuoka, T.; Samson, J. A. R.

    1979-01-01

    The molecular photoionization, dissociative photoionization and double photoionization cross sections for CO2 were measured from their onsets down to 90 A by using various combinations of mass spectrometers (a coincidence time-of-flight mass spectrometer and a magnetic mass spectrometer) and light sources (synchrotron radiation, and glow and spark discharge). It is concluded that the one broad peak and the three shoulders in the total adsorption cross section curve between 640 and 90 A are caused completely by dissociative ionization processes. Several peaks observed in the cross section curve for the total fragmentation CO(+)3, O(+) and C(+) are compared with those in the photoelectron spectrum reported for CO2.

  2. An unambiguous signature in molecular frame photoelectron angular distributions of core hole localization in fluorine K-edge photoionization of CF4

    NASA Astrophysics Data System (ADS)

    McCurdy, C. W.; Rescigno, T. N.; Trevisan, C. S.; Lucchese, R. R.

    2016-05-01

    Molecular Frame Photoelectron Angular Distributions (MFPADs) are calculated using the Complex Kohn variational method for core-hole ionization of the carbon and fluorines in CF4 at photoelectron energies below 15 eV. The angular distributions for localized versus delocalized core-hole creation on the four equivalent fluorines are radically different. A strong propensity for the dissociation to take place via the mechanism hν +CF4 -->CF 4 + +e- -->CF 3 + +F(1s-1) -->CF 3 + +F+ + 2e- in which a core excited neutral fluorine atom ionizes during or after dissociation creates the conditions for experimental observation of core hole localization. Comparison with recent unpublished experiments at the Advanced Light Source that measured the Recoil Frame Photoelectron Angular Distributions (averaged over CF3 rotations around the recoil axis) for fluorine K-edge ionization gives unambiguous evidence that these experiments directly observed the creation of an almost completely localized core hole on the dissociating fluorine atom when the molecule was initially photoionized. Work supported by USDOE, OBES Chemical Sciences, Geosciences, and Biosciences Division.

  3. Double momentum spectrometer for ion-electron vector correlations in dissociative photoionization

    SciTech Connect

    Bomme, C.; Guillemin, R.; Marin, T.; Journel, L.; Marchenko, T.; Pilette, B.; Avila, A.; Ringuenet, H.; Kushawaha, R. K.; Simon, M.; Dowek, D.; Trcera, N.

    2013-10-15

    We have developed a new momentum spectrometer dedicated to momentum vector correlations in the context of deep core photoionization of atomic and molecular species in the gas phase. In this article, we describe the design and operation of the experimental setup. The capabilities of the apparatus are illustrated with a set of measurements done on the sulphur core 1s photoionization of gas-phase CS{sub 2}.

  4. Double momentum spectrometer for ion-electron vector correlations in dissociative photoionization

    NASA Astrophysics Data System (ADS)

    Bomme, C.; Guillemin, R.; Marin, T.; Journel, L.; Marchenko, T.; Dowek, D.; Trcera, N.; Pilette, B.; Avila, A.; Ringuenet, H.; Kushawaha, R. K.; Simon, M.

    2013-10-01

    We have developed a new momentum spectrometer dedicated to momentum vector correlations in the context of deep core photoionization of atomic and molecular species in the gas phase. In this article, we describe the design and operation of the experimental setup. The capabilities of the apparatus are illustrated with a set of measurements done on the sulphur core 1s photoionization of gas-phase CS2.

  5. Triply Differential Studies of Atomic and Molecular Photoionization Using Synchrotron Radiation.

    DTIC Science & Technology

    1985-10-17

    B. West, E. D. Poliakoff , and J. L. Dehmer, "Wavelength and Vibrational- State Dependence of Photoelectron Angular Distributions. Resonance Effects in...Dehmer, "Triply-Differential Photoelectron Studies of Molecular Autoionization Profiles," Phys. Rev. Letters 46, 22 (1981). 3. E. D. Poliakoff , J. L...Resonance in Xe," J. Phys. B 13, L693 (1980). 9. E. D. Poliakoff , P. M. Dehmer, J. L. Dehmer, and R. L. Stockbauer, "The Photoelectron Spectrum of Xe by the

  6. Measurement of the photoionization spectra and ionization thresholds of the H sub 2 CN and D sub 2 CN radicals

    SciTech Connect

    Nesbitt, F.L.; Marston, G.; Stief, L.J. ); Wickramaaratchi, M.A.; Tao, W.; Klemm, R.B. )

    1991-10-03

    The photoionization spectra of the H{sub 2}CN and D{sub 2}CN radicals were obtained by photoionization mass spectroscopy (PIMS) using synchrotron radiation. The radicals were generated by the reaction of N with CH{sub 3} and CD{sub 3}, respectively. For both H{sub 2}CN and D{sub 2}CN a prominent feature was observed near 118.6 nm (10.5 eV) and the ionization threshold was determined to be 9.4 {plus minus} 0.1 eV; both features provide additional signatures for identifying H{sub 2}CN in complex systems. By use of a corrected value for {Delta}H{sub f} (H{sub 2}CN) derived from a recent electron affinity measurement and other available measured or calculated thermochemical quantities for H{sub 2}CN and HCNH radicals and radical ions, a value of 10.8 {plus minus} 0.6 eV for the ionization energy of H{sub 2}CN was derived. The much lower value derived for the ionization energy of HCNH (6.8 and 7.0 eV for the cis and trans isomers, respectively) is consistent with the product of the N + CH{sub 3} reaction being the H{sub 2}CN isomer and not HCNH. The ionization threshold observed at 9.4 eV is attributed to autoionization arising from high Rydberg states of H{sub 2}CN which couple into vibrationally excited states of the linear HCNH{sup +} ground state of the ion. Also discussed are the roles of the H{sub 2}CN radical and HCNH{sup +} radical ion in the chemistry of the atmosphere of Titan and in interstellar clouds.

  7. Merging quantum-chemistry with B-splines to describe molecular photoionization

    NASA Astrophysics Data System (ADS)

    Argenti, L.; Marante, C.; Klinker, M.; Corral, I.; Gonzalez, J.; Martin, F.

    2016-05-01

    Theoretical description of observables in attosecond pump-probe experiments requires a good representation of the system's ionization continuum. For polyelectronic atoms and molecules, however, this is still a challenge, due to the complicated short-range structure of correlated electronic wavefunctions. Whereas quantum chemistry packages (QCP) implementing sophisticated methods to compute bound electronic molecular states are well established, comparable tools for the continuum are not widely available yet. To tackle this problem, we have developed a new approach that, by means of a hybrid Gaussian-B-spline basis, interfaces existing QCPs with close-coupling scattering methods. To illustrate the viability of this approach, we report results for the multichannel ionization of the helium atom and of the hydrogen molecule that are in excellent agreement with existing accurate benchmarks. These findings, together with the flexibility of QCPs, make of this approach a good candidate for the theoretical study of the ionization of poly-electronic systems. FP7/ERC Grant XCHEM 290853.

  8. Does feedback help or hinder star formation? The effect of photoionization on star formation in giant molecular clouds

    NASA Astrophysics Data System (ADS)

    Shima, Kazuhiro; Tasker, Elizabeth J.; Habe, Asao

    2017-05-01

    We investigated the effect of photoionizing feedback inside turbulent star-forming clouds, comparing the resultant star formation in both idealized profiles and more realistic cloud structures drawn from a global galaxy simulation. We performed a series of numerical simulations that compared the effect of star formation alone, photoionization and photoionization plus supernovae feedback. In the idealized cloud, photoionization suppresses gas fragmentation at early times, resulting in the formation of more massive stars and an increase in the star formation efficiency. At later times, the dispersal of the dense gas causes the radiative feedback effect to switch from positive to negative as the star formation efficiency drops. In the cloud extracted from the global simulation, the initial cloud is heavily fragmented prior to the stellar-feedback beginning and is largely structurally unaffected by the late injection of radiation energy. The result is a suppression of the star formation. We conclude that the efficiency of feedback is heavily dependent on the gas structure, with negative feedback dominating when the density is high.

  9. Mass-Selective Laser Photoionization.

    ERIC Educational Resources Information Center

    Smalley, R. E.

    1982-01-01

    Discusses the nature and applications of mass-selective laser photoionization. The ionization can be done with a single intense laser pulse lasting a few billionths of a second with no molecular fragmentation. Applications focus on: (1) benzene clusters, excimers, and exciplexes; (2) metal clusters; and (3) triplet formation and decay. (Author/JN)

  10. Mass-Selective Laser Photoionization.

    ERIC Educational Resources Information Center

    Smalley, R. E.

    1982-01-01

    Discusses the nature and applications of mass-selective laser photoionization. The ionization can be done with a single intense laser pulse lasting a few billionths of a second with no molecular fragmentation. Applications focus on: (1) benzene clusters, excimers, and exciplexes; (2) metal clusters; and (3) triplet formation and decay. (Author/JN)

  11. Photoionization Efficiencies of Five Polycyclic Aromatic Hydrocarbons.

    PubMed

    Johansson, K Olof; Campbell, Matthew F; Elvati, Paolo; Schrader, Paul E; Zádor, Judit; Richards-Henderson, Nicole K; Wilson, Kevin R; Violi, Angela; Michelsen, Hope A

    2017-06-15

    We have measured photoionization-efficiency curves for pyrene, fluoranthene, chrysene, perylene, and coronene in the photon energy range of 7.5-10.2 eV and derived their photoionization cross-section curves in this energy range. All measurements were performed using tunable vacuum ultraviolet (VUV) radiation generated at the Advanced Light Source synchrotron at Lawrence Berkeley National Laboratory. The VUV radiation was used for photoionization, and detection was performed using a time-of-flight mass spectrometer. We measured the photoionization efficiency of 2,5-dimethylfuran simultaneously with those of pyrene, fluoranthene, chrysene, perylene, and coronene to obtain references of the photon flux during each measurement from the known photoionization cross-section curve of 2,5-dimethylfuran.

  12. Photoionization Efficiencies of Five Polycyclic Aromatic Hydrocarbons

    DOE PAGES

    Johansson, K. Olof; Campbell, Matthew F.; Elvati, Paolo; ...

    2017-05-18

    We have measured photoionization-efficiency curves for pyrene, fluoranthene, chrysene, perylene, and coronene in the photon energy range of 7.5-10.2 eV and derived their photoionization cross-section curves in this energy range. All measurements were performed using tunable vacuum ultraviolet (VUV) radiation generated at the Advanced Light Source synchrotron at Lawrence Berkeley National Laboratory. The VUV radiation was used for photoionization, and detection was performed using a time-of-flight mass spectrometer. We measured the photoionization efficiency of 2,5-dimethylfuran simultaneously with those of pyrene, fluoranthene, chrysene, perylene, and coronene to obtain references of the photon flux during each measurement from the known photoionization cross-sectionmore » curve of 2,5- dimethylfuran.« less

  13. Calculated photoionization cross sections using Quantemol-N

    NASA Astrophysics Data System (ADS)

    Brigg, Will J.; Harvey, Alex G.; Dzarasova, Anna; Mohr, Sebastian; Brambila, Danilo S.; Morales, Felipe; Smirnova, Olga; Tennyson, Jonathan

    2015-06-01

    Quantemol-N is an expert system designed to run the widely used UK Molecular R-matrix code (UKRMol). Originally designed to consider electron-molecule collision problems, here we present an extension to treat molecular photoionization. Sample results are given for the photoionization of molecular nitrogen and methane. Comparisons are made with experimental results showing good agreement.

  14. Synchrotron Photoionization Mass Spectrometry Measurements of Kinetics and Product Formation in the Allyl Radical (H2CCHCH2)Self Reaction

    NASA Technical Reports Server (NTRS)

    Selby, Talitha M.; Melini, giovanni; Goulay, Fabien; Leone, Stephen R.; Fahr, Askar; Taatjes, Craig A.; Osborn, David L.

    2008-01-01

    Product channels for the self-reaction of the resonance-stabilized allyl radical, C3H5 + C3H5, have been studied with isomeric specificity at temperatures from 300-600 K and pressures from 1-6 Torr using time-resolved multiplexed photoionization mass spectrometry. Under these conditions 1,5-hexadiene was the only C6H10 product isomer detected. The lack of isomerization of the C6H10 product is in marked contrast to the C6H6 product in the related C3H3 + C3H3 reaction, and is due to the more saturated electronic structure of the C6H10 system. The disproportionation product channel, yielding allene + propene, was also detected, with an upper limit on the branching fraction relative to recombination of 0.03. Analysis of the allyl radical decay at 298 K yielded a total rate coefficient of (2.7 +/- 0.8) x 10(exp -11) cu cm/molecule/s, in good agreement with pre.vious experimental measurements using ultraviolet kinetic absorption spectroscopy and a recent theoretical determination using variable reaction coordinate transition state theory. This result provides independent indirect support for the literature value of the allyl radical ultraviolet absorption cross-section near 223 nm.

  15. Absolute measurements of photoabsorption, Photoionization, and photodissociation cross sections of SiH4 and Si2H6 in the 13-22 eV region

    NASA Astrophysics Data System (ADS)

    Kameta, Kosei; Ukai, Masatoshi; Terazawa, Norihisa; Nagano, Kazunori; Chikahiro, Yuji; Kouchi, Norihuki; Hatano, Yoshihiko; Tanaka, Kenichiro

    1992-07-01

    The absolute values of the photoabsorption cross sections and photoionization quantum yields of silane and disilane have been measured in the 13-22 eV region. Using these values, we have evaluated the absolute cross sections of the photoionization and neutral dissociation. The individual structures observed in the cross section spectra have been interpreted in terms of the characters of superexcited states with strong emphasis on the neutral dissociation. The 3a1-1σ*(t2) state of silane presenting a broad peak at around 14.6 eV in an absorption cross section is shown to be strongly dissociative, whereas Rydberg series to the (3a1)-1 limit showing up vibrational structures between 16 and 18 eV predominantly undergo fast autoionization decay. A general importance of competition between autoionization and neutral dissociation is indicated of disilane in much higher energy region than the first ionization potential.

  16. Ion Storage Ring Measurements of Low Temperature Dielectronic Recombination Rate Coefficients for Modeling X-Ray Photoionized Cosmic Plasmas

    NASA Technical Reports Server (NTRS)

    Savin, D. W.; Gwinner, G.; Schwalm, D.; Wolf, A.; Mueller, A.; Schippers, S.

    2002-01-01

    Low temperature dielectronic recombination (DR) is the dominant recombination mechanism for most ions in X-ray photoionized cosmic plasmas. Reliably modeling and interpreting spectra from these plasmas requires accurate low temperature DR rate Coefficients. Of particular importance are the DR rate coefficients for the iron L-shell ions (Fe XVII-Fe XXIV). These ions are predicted to play an important role in determining the thermal structure and line emission of X-ray photoionized plasmas, which form in the media surrounding accretion powered sources such as X-ray binaries (XRBs), active galactic nuclei (AGN), and cataclysmic variables (Savin et al., 2000). The need for reliable DR data of iron L-shell ions has become particularly urgent after the launches of Chandra and XMM-Newton. These satellites are now providing high-resolution X-ray spectra from a wide range of X-ray photoionized sources. Interpreting the spectra from these sources requires reliable DR rate coefficients. However, at the temperatures relevant, for X-ray photoionized plasmas, existing theoretical DR rate coefficients can differ from one another by factors of two to orders of magnitudes.

  17. Production of C2H4Cl+ by dissociative photoionization of weak molecular complexes in C2H4 + HCl mixtures

    NASA Astrophysics Data System (ADS)

    Walters, E. A.; Grover, J. R.; Arneberg, D. L.; Santandrea, C. J.; White, M. G.

    1990-12-01

    The photoionization efficiency (PIE) spectrum from 600 to 1200 Å for the production of the ion C2H4Cl+ by dissociative photoionization of the products of room-temperature jet expansions of a 1:4 mixture of C2H4 and HCl was measured at several nozzle pressures. The results were resolved into the PIE yield curve for the heterodimer process C2H4·HCl+ hv→C2H4Cl++H+ e. This reaction is necessarily characterized by a large change in geometry between neutral complex and ionic product. The observed spectrum exhibits an unusual and conspicuous peak at 15.2 eV that is characterized by a sharp cutoff to the high energy side. This feature points to the onset of strongly nonstatistical channels for the production of C2H4Cl+ at this energy such that product formation proceeds through very few states. The observed onset of C2H4Cl+ at 11.92±0.24 eV is 17±6 kcal mol-1 above the true threshold. An important conclusion is that at all energies above the onset the yield of dissociative ionization of the heterodimer to the cation C2H4Cl+ is determined by dynamical factors.

  18. Photoionization of the cerium isonuclear sequence and cerium endohedral fullerene

    NASA Astrophysics Data System (ADS)

    Habibi, Mustapha

    This dissertation presents an experimental photoionization study of the cerium isonuclear sequence ions in the energy range of the 4d inner-shell giant resonance. In addition, single and double photoionization and photofragmentation cross sections of the cerium endohedral ion Ce C+82 were also measured and studied in the 4d excitation-ionization energy range of cerium. Relative and absolute cross-section measurements were performed at undulator beamline 10.0.1 of the Advanced Light Source (ALS) for nine parent cerium ions: Ce+ - Ce9+. Double-to-single ionization cross-section ratios were measured for photoionization of the endohedral Ce C+82 and empty fullerene C C+82 molecular ions. The merged ion and photon beams technique was used to conduct the experiments. Multiconfiguration Hartree-Fock calculations were performed as an aid to interpret the experimental data. Four Rydberg series for 4d → nf (n ≥ 4) and 4d → np (n ≥ 6) autoionizing excitations were assigned using the quantum defect theory for the Ce3+ photoionization cross section. The experimental data show the collapse of the nf wavefunctions (n ≥ 4) with increasing ionization stage as outer-shell electrons are stripped from the parent ion. The nf orbital collapse occurs partially for Ce2+ and Ce3+ ion and completely for Ce4+, where these wavefunctions penetrate the core region of the ion. A strong contribution to the total oscillator strength was observed in the double and triple photoionization channels for low charge states (Ce +, Ce2+, and Ce3+), whereas most of the 4d excitations of the higher charge states decay by ejection of one electron.

  19. Near-threshold absolute photoionization cross-sections of some reaction intermediates in combustion

    NASA Astrophysics Data System (ADS)

    Wang, Juan; Yang, Bin; Cool, Terrill A.; Hansen, Nils; Kasper, Tina

    2008-02-01

    The use of photoionization mass spectrometry for the development of quantitative kinetic models for the complex combustion chemistry of both conventional hydrocarbon fuels and oxygenated biofuels requires near-threshold measurements of absolute photoionization cross-sections for numerous reaction intermediates. Near-threshold absolute cross-sections for molecular and dissociative photoionization for 20 stable reaction intermediates (methane, ethane, propane, n-butane, cyclopropane, methylcyclopentane, 1-butene, cis-2-butene, isobutene, 1-pentene, cyclohexene, 3,3-dimethyl-1-butene, 1,3-hexadiene, 1,3-cyclohexadiene, methyl acetate, ethyl acetate, tetrahydrofuran, propanal, 1-butyne, 2-butyne) are presented. Previously measured total photoionization cross-sections for 9 of these molecules are in good agreement with the present results. The measurements are performed with photoionization mass spectrometry (PIMS) using a monochromated VUV synchrotron light source with an energy resolution of 40 meV (fwhm) comparable to that used for flame-sampling molecular beam PIMS studies of flame chemistry and reaction kinetics.

  20. Complex decay patterns in atomic core photoionization disentangled by ion-recoil measurements

    SciTech Connect

    Guillemin, Renaud; Bomme, Cedric; Marin, Thierry; Journel, Loic; Marchenko, Tatiana; Kushawaha, Rajesh K.; Piancastelli, Maria Novella; Simon, Marc; Trcera, Nicolas

    2011-12-15

    Following core 1s ionization and resonant excitation of argon atoms, we measure the recoil energy of the ions due to momentum conservation during the emission of Auger electrons. We show that such ion momentum spectroscopy can be used to disentangle to some degree complex decay patterns, involving both radiative and nonradiative decays.

  1. Measurement of relative K X-ray intensity ratio following radioactive decay and photoionization

    NASA Astrophysics Data System (ADS)

    Yalçın, P.

    2007-01-01

    The measurements of the K X-ray intensity ratio I(Kα2/Kα1), I(Kβ1/Kα1) and I(Kβ/Kα) for elements V, Mn, Zn, Tc, Ru, Cd, Xe, Ba, Cs, Hg and Rn were experimentally determined both by photon excitation, in which 59.5 keV γ-rays from a 241Am and 123.6 keV γ-rays from a 60Co were used, and following the radioactive decay of 51Cr, 55Fe, 67Ga, 99Tc, 111In, 131I, 133Ba, 133Xe, 137Cs, 201Tl and 226Ra. K X-rays emitted by samples were counted by a Si(Li) detector with resolution 160 eV at 5.9 keV. Obtained values were compared with the theoretical values. It was observed that present values agree with the previous theoretical and other experimental results.

  2. Photoionization of sodium clusters

    SciTech Connect

    Peterson, K.I.; Dao, P.D.; Farley, R.W.; Castleman, A.W. Jr.

    1984-03-01

    Sodium clusters, Na/sub x/ (2< or =x< or =8), were produced in a supersonic jet by coexpansion with argon and subjected to analysis via photoionization coupled with mass spectrometry. The present measurements, made at somewhat higher resolution than earlier literature studies, yield ionization potentials in excellent agreement for x = 1 to 4 and x = 7, and reveal heretofore unreported structure in the post-threshold spectra. The present measurements enable a more definitive assignment of the ionization potentials, giving a lower value for x = 6 and pointing to lower ones for x = 5 and 8. The frequently discussed odd--even alternation in ionization potentials is no longer evident beyond the pentamer. Values for the binding energies of Na to Na/sup +//sub x/ (3< or =x< or =8) are deduced.

  3. PHOTOIONIZATION IN THE SOLAR WIND

    SciTech Connect

    Landi, E.; Lepri, S. T.

    2015-10-20

    In this work we investigate the effects of photoionization on the charge state composition of the solar wind. Using measured solar EUV and X-ray irradiance, the Michigan Ionization Code and a model for the fast and slow solar wind, we calculate the evolution of the charge state distribution of He, C, N, O, Ne, Mg, Si, S, and Fe with and without including photoionization for both types of wind. We find that the solar radiation has significant effects on the charge state distribution of C, N, and O, causing the ionization levels of these elements to be higher than without photoionization; differences are largest for oxygen. The ions commonly observed for elements heavier than O are much less affected, except in ICMEs where Fe ions more ionized than 16+ can also be affected by the solar radiation. We also show that the commonly used O{sup 7+}/O{sup 6+} density ratio is the most sensitive to photoionization; this sensitivity also causes the value of this ratio to depend on the phase of the solar cycle. We show that the O{sup 7+}/O{sup 6+} ratio needs to be used with caution for solar wind classification and coronal temperature estimates, and recommend the C{sup 6+}/C{sup 4+} ratio for these purposes.

  4. Alignment of photoions far from threshold

    NASA Astrophysics Data System (ADS)

    Das, Romith; Wu, Chuanyong; Mihill, A. G.; Poliakoff, E. D.; Wang, Kwanghsi; McKoy, V.

    1994-09-01

    We present results of measurements and calculations of the alignment for CO+(B 2Σ+) photoions over an extended energy range (0≤Ek≤210 eV). The polarization of CO+(B 2Σ+→X 2Σ+) fluorescence indicates that the photoions retain significant alignment even at high energies. Agreement between the measured and calculated polarization of the fluorescence is excellent.

  5. Molecular Isomer Identification of Titan's Tholins Organic Aerosols by Photoelectron/Photoion Coincidence Spectroscopy Coupled to VUV Synchrotron Radiation.

    PubMed

    Cunha de Miranda, Barbara; Garcia, Gustavo A; Gaie-Levrel, François; Mahjoub, Ahmed; Gautier, Thomas; Fleury, Benjamin; Nahon, Laurent; Pernot, Pascal; Carrasco, Nathalie

    2016-08-25

    The chemical composition of Titan organic haze is poorly known. To address this issue, laboratory analogues named tholins are synthesized and analyzed by methods often requiring an extraction process in a carrier solvent. These methods exclude the analysis of the insoluble tholins' fraction and assume a hypothetical chemical equivalence between soluble and insoluble fractions. In this work, we present a powerful complementary analysis method recently developed on the DESIRS VUV synchrotron beamline at SOLEIL. It involves soft pyrolysis of tholins at ∼230 °C and electron/ion coincidence analysis of the emitted volatile compounds photoionized by tunable synchrotron radiation. By comparison with reference photoelectron spectra (PES), the spectral information collected on the detected molecules yields their isomeric structure. The method is more readily applied to light species (m/z ≤ 69), while for heavier ones, the number of possibilities and the lack of PES reference spectra in the literature limit its analysis. A notable pattern in the analyzed tholins is the presence of species containing adjacent doubly bonded N atoms, which might be a signature of heterogeneous incorporation of N2 in tholins.

  6. The Multiplexed Chemical Kinetic Photoionization Mass Spectrometer: A New Approach To Isomer-resolved Chemical Kinetics

    SciTech Connect

    Osborne, David L.; Zou, Peng; Johnsen, Howard; Hayden, Carl C.; Taatjes, Craig A.; Knyazev, Vadim D.; North, Simon W.; Peterka, Darcy S.; Ahmed, Musahid; Leone, Stephen R.

    2008-08-28

    We have developed a multiplexed time- and photon-energy?resolved photoionizationmass spectrometer for the study of the kinetics and isomeric product branching of gasphase, neutral chemical reactions. The instrument utilizes a side-sampled flow tubereactor, continuously tunable synchrotron radiation for photoionization, a multi-massdouble-focusing mass spectrometer with 100percent duty cycle, and a time- and positionsensitive detector for single ion counting. This approach enables multiplexed, universal detection of molecules with high sensitivity and selectivity. In addition to measurement of rate coefficients as a function of temperature and pressure, different structural isomers can be distinguished based on their photoionization efficiency curves, providing a more detailed probe of reaction mechanisms. The multiplexed 3-dimensional data structure (intensity as a function of molecular mass, reaction time, and photoionization energy) provides insights that might not be available in serial acquisition, as well as additional constraints on data interpretation.

  7. Photoabsorption and photoionization cross sections for formaldehyde in the vacuum-ultraviolet energy range

    NASA Astrophysics Data System (ADS)

    Tanaka, H. K.; Prudente, F. V.; Medina, A.; Marinho, R. R. T.; Homem, M. G. P.; Machado, L. E.; Fujimoto, M. M.

    2017-03-01

    We report a theoretical-experimental investigation on the interaction of vacuum-ultraviolet radiation with formaldehyde (H2CO) in the gas phase. Experimentally, the absolute photoabsorption cross sections and the photoionization quantum yields were measured in the (11.0-21.5) eV range using the double-ion chamber technique. Also, the absolute photoionization and neutral-decay cross sections were derived from these data. In addition, in the same energy region, the dissociation pattern was obtained with a time-of-flight mass spectrometer using the photoelectron-photoion coincidence technique, and the absolute photoionization cross sections were derived for each ionic fragment observed. Moreover, theoretical photoionization cross sections were calculated for the ionization of the four outermost molecular valence orbitals (2b2, 1b1, 5a1, and 1b2) from the threshold to 35 eV. The calculations were performed using the iterative Schwinger variational method to solve the Lippmann-Schwinger equation in the exact static-exchange level of approximation. In general, there is a good agreement between our experimental and previous data reported in the literature. Our theoretical results show a fair qualitative agreement with the experimental data and with previous theoretical results. Above 20 eV, a better quantitative agreement with the experimental data is also observed.

  8. Photoionization of Ar VIII

    NASA Astrophysics Data System (ADS)

    Liang, Liang; Jiang, Wen-xian; Zhou, Chao

    2017-01-01

    The photoionization cross section, energy levels and widths of 22 Rydberg series (in the autoionization region) for Na-like Ar VIII were investigated by using of R-matrix method. The relativistic distorted-wave method is used to calculate the radial functions, and QB method of Quigly-Berrington [Quigley et al. 1998] is employed to calculate the resonance levels and widths. We have identified the formant in the figure of the photoionization cross section.

  9. Thermopower measurements in molecular junctions.

    PubMed

    Rincón-García, Laura; Evangeli, Charalambos; Rubio-Bollinger, Gabino; Agraït, Nicolás

    2016-08-07

    The measurement of thermopower in molecular junctions offers complementary information to conductance measurements and is becoming essential for the understanding of transport processes at the nanoscale. In this review, we discuss the recent advances in the study of the thermoelectric properties of molecular junctions. After presenting the theoretical background for thermoelectricity at the nanoscale, we review the experimental techniques for measuring the thermopower in these systems and discuss the main results. Finally, we consider the challenges in the application of molecular junctions in viable thermoelectric devices.

  10. Hyphenation of a carbon analyzer to photo-ionization mass spectrometry to unravel the organic composition of particulate matter on a molecular level.

    PubMed

    Grabowsky, Jana; Streibel, Thorsten; Sklorz, Martin; Chow, Judith C; Watson, John G; Mamakos, Athanasios; Zimmermann, Ralf

    2011-12-01

    The carbonaceous fraction of airborne particulate matter (PM) is of increasing interest due to the adverse health effects they are linked to. Its analytical ascertainment on a molecular level is still challenging. Hence, analysis of carbonaceous fractions is often carried out by determining bulk parameters such as the overall content of organic compounds (OC) and elemental carbon (EC) as well as the total carbon content, TC (sum of OC and EC), however, no information about the individual substances or substance classes, of which the single fractions consist can be obtained. In this work, a carbon analyzer and a photo-ionization time-of-flight mass spectrometer (PI-TOF-MS) were hyphenated to investigate individual compounds especially from the OC fractions. The carbon analyzer enables the stepwise heating of particle samples and provides the bulk parameters. With the PI-TOF-MS, it is possible to detect the organic compounds released during the single-temperature steps due to soft ionization and fast detection of the molecular ions. The hyphenation was designed, built up, characterized by standard substances, and applied to several kinds of samples, such as ambient aerosol, gasoline, and diesel emission as well as wood combustion emission samples. The ambient filter sample showed a strong impact of wood combustion markers. This was revealed by comparison to the product pattern of the similar analysis of pure cellulose and lignin and the wood combustion PM. At higher temperatures (450 °C), a shift to smaller molecules occurred due to the thermal decomposition of larger structures of oligomeric or polymeric nature comparable to lignocelluloses and similar oxygenated humic-like substances. Finally, particulate matter from gasoline and diesel containing 10% biodiesel vehicle exhaust has been analyzed. Gasoline-derived PM exhibited large polycyclic aromatic hydrocarbons, whereas diesel PM showed a much higher total organic content. The detected pattern revealed a strong

  11. Measurements of mass attenuation coefficients and determination of photoionization cross sections at energies across the Li (i=1-3) edges of 66Dy

    NASA Astrophysics Data System (ADS)

    Kaur, Rajnish; Kumar, Anil; Osan, Janos; Czyzycki, M.; Karydas, A. G.; Puri, Sanjiv

    2017-07-01

    The absolute values of the mass attenuation coefficients have been measured at sixty two photon energies across the Li (i=1-3) sub-shell absorption edges of 66Dy covering the region 7.6-14.0 keV in order to investigate the influence of near-edge processes on the attenuation coefficients. The present measured attenuation coefficients are found to be higher by up to 10% than the theoretical values evaluated from the computer code XCOM (Berger et al., 2010) and the self-consistent Dirac-Hartree-Slater (DHS) model based values tabulated by Chantler (1995) over the energy region 7.6-14.0 keV, except at energies in vicinity (few eV) of the Li (i=1-3) sub-shell absorption edge energies where the measured values are significantly higher (up to 37%) than both the sets of theoretical values. Further, the Li (i=1-3) sub-shell photoionization cross sections, (σLiP)exp, deduced from the present measured mass attenuation coefficients are compared with the non-relativistic Hartree-Fock-Slater (HFS) model based values tabulated by Scofield (1973) and those evaluated from the theoretical total photoionization attenuation coefficients tabulated by Chantler (1995). The deduced (σLiP)exp(i=1-3) values are found to be in better agreement with those evaluated from the tabulations given by Chantler (1995) than the values given by Scofield (1973) over the energy region 7.8 - 14.0 keV included in this study. However, at photon energies up to few eV above the Li edges, the deduced (σLiP)exp(i=1-3) values are found to be significantly higher (up to 32%) than both the sets of theoretical values.

  12. A photoelectron-photoion coincidence imaging apparatus for femtosecond time-resolved molecular dynamics with electron time-of-flight resolution of {sigma}=18 ps and energy resolution {delta}E/E=3.5%

    SciTech Connect

    Vredenborg, Arno; Roeterdink, Wim G.; Janssen, Maurice H. M.

    2008-06-15

    We report on the construction and performance of a novel photoelectron-photoion coincidence machine in our laboratory in Amsterdam to measure the full three-dimensional momentum distribution of correlated electrons and ions in femtosecond time-resolved molecular beam experiments. We implemented sets of open electron and ion lenses to time stretch and velocity map the charged particles. Time switched voltages are operated on the particle lenses to enable optimal electric field strengths for velocity map focusing conditions of electrons and ions separately. The position and time sensitive detectors employ microchannel plates (MCPs) in front of delay line detectors. A special effort was made to obtain the time-of-flight (TOF) of the electrons at high temporal resolution using small pore (5 {mu}m) MCPs and implementing fast timing electronics. We measured the TOF distribution of the electrons under our typical coincidence field strengths with a temporal resolution down to {sigma}=18 ps. We observed that our electron coincidence detector has a timing resolution better than {sigma}=16 ps, which is mainly determined by the residual transit time spread of the MCPs. The typical electron energy resolution appears to be nearly laser bandwidth limited with a relative resolution of {delta}E{sub FWHM}/E=3.5% for electrons with kinetic energy near 2 eV. The mass resolution of the ion detector for ions measured in coincidence with electrons is about {delta}m{sub FWHM}/m=1/4150. The velocity map focusing of our extended source volume of particles, due to the overlap of the molecular beam with the laser beams, results in a parent ion spot on our detector focused down to {sigma}=115 {mu}m.

  13. Vacuum ultraviolet (VUV) photoionization of small water clusters.

    PubMed

    Belau, Leonid; Wilson, Kevin R; Leone, Stephen R; Ahmed, Musahid

    2007-10-11

    Tunable vacuum ultraviolet (VUV) photoionization studies of water clusters are performed using 10-14 eV synchrotron radiation and analyzed by reflectron time-of-flight (TOF) mass spectrometry. Photoionization efficiency (PIE) curves for protonated water clusters (H2O)(n)H+ are measured with 50 meV energy resolution. The appearance energies of a series of protonated water clusters are determined from the photoionization threshold for clusters composed of up to 79 molecules. These appearance energies represent an upper limit of the adiabatic ionization energy of the corresponding parent neutral water cluster in the supersonic molecular beam. The experimental results show a sharp drop in the appearance energy for the small neutral water clusters (from 12.62 +/- 0.05 to 10.94 +/- 0.06 eV, for H2O and (H2O)4, respectively), followed by a gradual decrease for clusters up to (H2O)23 converging to a value of 10.6 eV (+/-0.2 eV). The dissociation energy to remove a water molecule from the corresponding neutral water cluster is derived through thermodynamic cycles utilizing the dissociation energies of protonated water clusters reported previously in the literature. The experimental results show a gradual decrease of the dissociation energy for removal of one water molecule for small neutral water clusters (3

  14. Molecular photoemission studies using synchrotron radiation

    SciTech Connect

    Truesdale, C.M.

    1983-04-01

    The angular distributions of photoelectrons and Auger electrons were measured by electron spectroscopy using synchrotron radiation. The experimental results are compared with theoretical calculations to interpret the electronic behavior of photoionization for molecular systems.

  15. Photoionization and Recombination

    NASA Technical Reports Server (NTRS)

    Nahar, Sultana N.

    2000-01-01

    Theoretically self-consistent calculations for photoionization and (e + ion) recombination are described. The same eigenfunction expansion for the ion is employed in coupled channel calculations for both processes, thus ensuring consistency between cross sections and rates. The theoretical treatment of (e + ion) recombination subsumes both the non-resonant recombination ("radiative recombination"), and the resonant recombination ("di-electronic recombination") processes in a unified scheme. In addition to the total, unified recombination rates, level-specific recombination rates and photoionization cross sections are obtained for a large number of atomic levels. Both relativistic Breit-Pauli, and non-relativistic LS coupling, calculations are carried out in the close coupling approximation using the R-matrix method. Although the calculations are computationally intensive, they yield nearly all photoionization and recombination parameters needed for astrophysical photoionization models with higher precision than hitherto possible, estimated at about 10-20% from comparison with experimentally available data (including experimentally derived DR rates). Results are electronically available for over 40 atoms and ions. Photoionization and recombination of He-, and Li-like C and Fe are described for X-ray modeling. The unified method yields total and complete (e+ion) recombination rate coefficients, that can not otherwise be obtained theoretically or experimentally.

  16. Flash-photoionized nebulae

    NASA Technical Reports Server (NTRS)

    Katz, J. I.

    1989-01-01

    Under conditions of high radiation intensity and low gas density, recombination may be neglected in determining the ionization state of a photoionized gas. Calculations of the ionization structure of nebulae in this 'flash-photoionized' regime are reported. Very hard spectra of ionizing ultraviolet radiation may be produced by filtration of the ionizing flux through a neutral hydrogen layer which preferentially absorbs photons just above the hydrogen photoionization threshold. Fluxes with these hard spectra produce gas layer in which helium is largely doubly ionized while hydrogen is largely neutral. Such a layer leads to anomalously high ratios of He II to H I recombination line strengths. These results are applied to the problem of the spectrum of the arc in the cluster of galaxies A370. It is found that the spectrum may possibly be reconciled with the light echo model.

  17. Flash-photoionized nebulae

    SciTech Connect

    Katz, J.I.

    1989-05-01

    Under conditions of high radiation intensity and low gas density, recombination may be neglected in determining the ionization state of a photoionized gas. Calculations of the ionization structure of nebulae in this 'flash-photoionized' regime are reported. Very hard spectra of ionizing ultraviolet radiation may be produced by filtration of the ionizing flux through a neutral hydrogen layer which preferentially absorbs photons just above the hydrogen photoionization threshold. Fluxes with these hard spectra produce gas layer in which helium is largely doubly ionized while hydrogen is largely neutral. Such a layer leads to anomalously high ratios of He II to H I recombination line strengths. These results are applied to the problem of the spectrum of the arc in the cluster of galaxies A370. It is found that the spectrum may possibly be reconciled with the light echo model. 25 refs.

  18. Atomic photoionization experiment by harmonic-generation spectroscopy

    NASA Astrophysics Data System (ADS)

    Frolov, M. V.; Sarantseva, T. S.; Manakov, N. L.; Fulfer, K. D.; Wilson, B. P.; Troß, J.; Ren, X.; Poliakoff, E. D.; Silaev, A. A.; Vvedenskii, N. V.; Starace, Anthony F.; Trallero-Herrero, C. A.

    2016-03-01

    Measurements of the high-order-harmonic generation yield of the argon (Ar) atom driven by a strong elliptically polarized laser field are shown to completely determine the field-free differential photoionization cross section of Ar, i.e., the energy dependence of both the angle-integrated photoionization cross section and the angular distribution asymmetry parameter.

  19. Double Photoionization Near Threshold

    NASA Technical Reports Server (NTRS)

    Wehlitz, Ralf

    2007-01-01

    The threshold region of the double-photoionization cross section is of particular interest because both ejected electrons move slowly in the Coulomb field of the residual ion. Near threshold both electrons have time to interact with each other and with the residual ion. Also, different theoretical models compete to describe the double-photoionization cross section in the threshold region. We have investigated that cross section for lithium and beryllium and have analyzed our data with respect to the latest results in the Coulomb-dipole theory. We find that our data support the idea of a Coulomb-dipole interaction.

  20. Vacuum Ultraviolet Photoionization of Complex Chemical Systems.

    PubMed

    Kostko, Oleg; Bandyopadhyay, Biswajit; Ahmed, Musahid

    2016-05-27

    Tunable vacuum ultraviolet (VUV) radiation coupled to mass spectrometry is applied to the study of complex chemical systems. The identification of novel reactive intermediates and radicals is revealed in flame, pulsed photolysis, and pyrolysis reactors, leading to the elucidation of spectroscopy, reaction mechanisms, and kinetics. Mass-resolved threshold photoelectron photoion coincidence measurements provide unprecedented access to vibrationally resolved spectra of free radicals present in high-temperature reactors. Photoionization measurements in water clusters, nucleic acid base dimers, and their complexes with water provide signatures of proton transfer in hydrogen-bonded and π-stacked systems. Experimental and theoretical methods to track ion-molecule reactions and fragmentation pathways in intermolecular and intramolecular hydrogen-bonded systems in sugars and alcohols are described. Photoionization of laser-ablated molecules, clusters, and their reaction products inform thermodynamics and spectroscopy that are relevant to astrochemistry and catalysis. New directions in coupling VUV radiation to interrogate complex chemical systems are discussed.

  1. Vacuum Ultraviolet Photoionization of Complex Chemical Systems

    NASA Astrophysics Data System (ADS)

    Kostko, Oleg; Bandyopadhyay, Biswajit; Ahmed, Musahid

    2016-05-01

    Tunable vacuum ultraviolet (VUV) radiation coupled to mass spectrometry is applied to the study of complex chemical systems. The identification of novel reactive intermediates and radicals is revealed in flame, pulsed photolysis, and pyrolysis reactors, leading to the elucidation of spectroscopy, reaction mechanisms, and kinetics. Mass-resolved threshold photoelectron photoion coincidence measurements provide unprecedented access to vibrationally resolved spectra of free radicals present in high-temperature reactors. Photoionization measurements in water clusters, nucleic acid base dimers, and their complexes with water provide signatures of proton transfer in hydrogen-bonded and π-stacked systems. Experimental and theoretical methods to track ion-molecule reactions and fragmentation pathways in intermolecular and intramolecular hydrogen-bonded systems in sugars and alcohols are described. Photoionization of laser-ablated molecules, clusters, and their reaction products inform thermodynamics and spectroscopy that are relevant to astrochemistry and catalysis. New directions in coupling VUV radiation to interrogate complex chemical systems are discussed.

  2. Intramolecular SN2 reaction caused by photoionization of benzene chloride-NH3 complex: direct ab initio molecular dynamics study.

    PubMed

    Tachikawa, Hiroto

    2006-01-12

    Ionization processes of chlorobenzene-ammonia 1:1 complex (PhCl-NH3) have been investigated by means of full dimensional direct ab initio molecular dynamics (MD) method, static ab initio calculations, and density functional theory (DFT) calculations. The static ab initio and DFT calculations of neutral PhCl-NH3 complex showed that one of the hydrogen atoms of NH3 orients toward a carbon atom in the para-position of PhCl. The dynamics calculation for ionization of PhCl-NH3 indicated that two reaction channels are competitive with each other as product channels: one is an intramolecular SN2 reaction expressed by a reaction scheme [PhCl-NH3]+-->SN2 intermediate complex-->PhNH3++Cl, and the other is ortho-NH3 addition complex (ortho complex) in which NH3 attacks the ortho-carbon of PhCl+ and the trajectory leads to a bound complex expressed by (PhCl-NH3)+. The mechanism of the ionization of PhCl-NH3 is discussed on the basis of the theoretical results.

  3. Measurement Frontiers in Molecular Biology

    NASA Astrophysics Data System (ADS)

    Laderman, Stephen

    2009-03-01

    Developments of molecular measurements and manipulations have long enabled forefront research in evolution, genetics, biological development and its dysfunction, and the impact of external factors on the behavior of cells. Measurement remains at the heart of exciting and challenging basic and applied problems in molecular and cell biology. Methods to precisely determine the identity and abundance of particular molecules amongst a complex mixture of similar and dissimilar types require the successful design and integration of multiple steps involving biochemical manipulations, separations, physical probing, and data processing. Accordingly, today's most powerful methods for characterizing life at the molecular level depend on coordinated advances in applied physics, biochemistry, chemistry, computer science, and engineering. This is well illustrated by recent approaches to the measurement of DNA, RNA, proteins, and intact cells. Such successes underlie well founded visions of how molecular biology can further assist in answering compelling scientific questions and in enabling the development of remarkable advances in human health. These visions, in turn, are motivating the interdisciplinary creation of even more comprehensive measurements. As a further and closely related consequence, they are motivating innovations in the conceptual and practical approaches to organizing and visualizing large, complex sets of interrelated experimental results and distilling from those data compelling, informative conclusions.

  4. Simulations of light induced processes in water based on ab initio path integrals molecular dynamics. II. Photoionization.

    PubMed

    Svoboda, Ondřej; Ončák, Milan; Slavíček, Petr

    2011-10-21

    We have applied ab initio based reflection principle to simulate photoelectron spectra of small water clusters, ranging from monomer to octamer. The role of quantum and thermal effects on the structure of the water photoelectron spectra is discussed within the ab initio path integral molecular dynamics (PIMD) framework. We have used the PIMD method with up to 40 beads to sample the ground state quantum distribution at temperature T = 180 K. We have thoroughly tested the performance of various density functionals (B3LYP, BHandHLYP, M06HF, BNL, LC-ωPBE, and CAM-B3LYP) for the ionization process description. The benchmarking based on a comparison of simulated photoelectron spectra to experimental data and high level equation-of-motion ionization potential coupled clusters with singles and doubles calculations has singled out the BHandHLYP and LC-ωPBE functionals as the most reliable ones for simulations of light induced processes in water. The good performance of the density functional theory functionals to model the water photoelectron spectra also reflects their ability to reliably describe open shell excited states. The width of the photoelectron spectrum converges quickly with the cluster size as it is controlled by specific interactions of local character. The peak position is, on the other hand, defined by long-range non-specific solvent effects; it therefore only slowly converges to the corresponding bulk value. We are able to reproduce the experimental valence photoelectron spectrum of liquid water within the combined model of the water octamer embedded in a polarizable dielectric continuum. We demonstrate that including the long-range polarization and the state-specific treatment of the solvent response are needed for a reliable liquid water ionization description. © 2011 American Institute of Physics

  5. Simulations of light induced processes in water based on ab initio path integrals molecular dynamics. II. Photoionization

    NASA Astrophysics Data System (ADS)

    Svoboda, Ondřej; Ončák, Milan; Slavíček, Petr

    2011-10-01

    We have applied ab initio based reflection principle to simulate photoelectron spectra of small water clusters, ranging from monomer to octamer. The role of quantum and thermal effects on the structure of the water photoelectron spectra is discussed within the ab initio path integral molecular dynamics (PIMD) framework. We have used the PIMD method with up to 40 beads to sample the ground state quantum distribution at temperature T = 180 K. We have thoroughly tested the performance of various density functionals (B3LYP, BHandHLYP, M06HF, BNL, LC-ωPBE, and CAM-B3LYP) for the ionization process description. The benchmarking based on a comparison of simulated photoelectron spectra to experimental data and high level equation-of-motion ionization potential coupled clusters with singles and doubles calculations has singled out the BHandHLYP and LC-ωPBE functionals as the most reliable ones for simulations of light induced processes in water. The good performance of the density functional theory functionals to model the water photoelectron spectra also reflects their ability to reliably describe open shell excited states. The width of the photoelectron spectrum converges quickly with the cluster size as it is controlled by specific interactions of local character. The peak position is, on the other hand, defined by long-range non-specific solvent effects; it therefore only slowly converges to the corresponding bulk value. We are able to reproduce the experimental valence photoelectron spectrum of liquid water within the combined model of the water octamer embedded in a polarizable dielectric continuum. We demonstrate that including the long-range polarization and the state-specific treatment of the solvent response are needed for a reliable liquid water ionization description.

  6. Photoionization mass spectrometric measurements of initial reaction pathways in low-temperature oxidation of 2,5-dimethylhexane.

    PubMed

    Rotavera, Brandon; Zádor, Judit; Welz, Oliver; Sheps, Leonid; Scheer, Adam M; Savee, John D; Akbar Ali, Mohamad; Lee, Taek Soon; Simmons, Blake A; Osborn, David L; Violi, Angela; Taatjes, Craig A

    2014-11-06

    Product formation from R + O2 reactions relevant to low-temperature autoignition chemistry was studied for 2,5-dimethylhexane, a symmetrically branched octane isomer, at 550 and 650 K using Cl-atom initiated oxidation and multiplexed photoionization mass spectrometry (MPIMS). Interpretation of time- and photon-energy-resolved mass spectra led to three specific results important to characterizing the initial oxidation steps: (1) quantified isomer-resolved branching ratios for HO2 + alkene channels; (2) 2,2,5,5-tetramethyltetrahydrofuran is formed in substantial yield from addition of O2 to tertiary 2,5-dimethylhex-2-yl followed by isomerization of the resulting ROO adduct to tertiary hydroperoxyalkyl (QOOH) and exhibits a positive dependence on temperature over the range covered leading to a higher flux relative to aggregate cyclic ether yield. The higher relative flux is explained by a 1,5-hydrogen atom shift reaction that converts the initial primary alkyl radical (2,5-dimethylhex-1-yl) to the tertiary alkyl radical 2,5-dimethylhex-2-yl, providing an additional source of tertiary alkyl radicals. Quantum-chemical and master-equation calculations of the unimolecular decomposition of the primary alkyl radical reveal that isomerization to the tertiary alkyl radical is the most favorable pathway, and is favored over O2-addition at 650 K under the conditions herein. The isomerization pathway to tertiary alkyl radicals therefore contributes an additional mechanism to 2,2,5,5-tetramethyltetrahydrofuran formation; (3) carbonyl species (acetone, propanal, and methylpropanal) consistent with β-scission of QOOH radicals were formed in significant yield, indicating unimolecular QOOH decomposition into carbonyl + alkene + OH.

  7. Photoionization mass spectrometric measurements of initial reaction pathways in low-temperature oxidation of 2,5-dimethylhexane

    DOE PAGES

    Rotavera, Brandon; Zádor, Judit; Welz, Oliver; ...

    2014-09-19

    The product formation from R + O2 reactions relevant to low-temperature autoignition chemistry was studied for 2,5-dimethylhexane, a symmetrically branched octane isomer, at 550 and 650 K using Cl-atom initiated oxidation and multiplexed photoionization mass spectrometry (MPIMS). The interpretation of time- and photon-energy-resolved mass spectra led to three specific results important to characterizing the initial oxidation steps: (1) quantified isomer-resolved branching ratios for HO2 + alkene channels; (2) 2,2,5,5-tetramethyltetrahydrofuran is formed in substantial yield from addition of O2 to tertiary 2,5-dimethylhex-2-yl followed by isomerization of the resulting ROO adduct to tertiary hydroperoxyalkyl (QOOH) and exhibits a positive dependence on temperaturemore » over the range covered leading to a higher flux relative to aggregate cyclic ether yield. The higher relative flux is explained by a 1,5-hydrogen atom shift reaction that converts the initial primary alkyl radical (2,5-dimethylhex-1-yl) to the tertiary alkyl radical 2,5-dimethylhex-2-yl, providing an additional source of tertiary alkyl radicals. Furthermore, quantum-chemical and master-equation calculations of the unimolecular decomposition of the primary alkyl radical reveal that isomerization to the tertiary alkyl radical is the most favorable pathway, and is favored over O2-addition at 650 K under the conditions herein. The isomerization pathway to tertiary alkyl radicals therefore contributes an additional mechanism to 2,2,5,5-tetramethyltetrahydrofuran formation; (3) carbonyl species (acetone, propanal, and methylpropanal) consistent with β-scission of QOOH radicals were formed in significant yield, indicating unimolecular QOOH decomposition into carbonyl + alkene + OH.« less

  8. Photoionization mass spectrometric measurements of initial reaction pathways in low-temperature oxidation of 2,5-dimethylhexane

    SciTech Connect

    Rotavera, Brandon; Zádor, Judit; Welz, Oliver; Sheps, Leonid; Scheer, Adam M.; Savee, John D.; Akbar Ali, Mohamad; Lee, Taek Soon; Simmons, Blake A.; Osborn, David L.; Violi, Angela; Taatjes, Craig A.

    2014-09-19

    The product formation from R + O2 reactions relevant to low-temperature autoignition chemistry was studied for 2,5-dimethylhexane, a symmetrically branched octane isomer, at 550 and 650 K using Cl-atom initiated oxidation and multiplexed photoionization mass spectrometry (MPIMS). The interpretation of time- and photon-energy-resolved mass spectra led to three specific results important to characterizing the initial oxidation steps: (1) quantified isomer-resolved branching ratios for HO2 + alkene channels; (2) 2,2,5,5-tetramethyltetrahydrofuran is formed in substantial yield from addition of O2 to tertiary 2,5-dimethylhex-2-yl followed by isomerization of the resulting ROO adduct to tertiary hydroperoxyalkyl (QOOH) and exhibits a positive dependence on temperature over the range covered leading to a higher flux relative to aggregate cyclic ether yield. The higher relative flux is explained by a 1,5-hydrogen atom shift reaction that converts the initial primary alkyl radical (2,5-dimethylhex-1-yl) to the tertiary alkyl radical 2,5-dimethylhex-2-yl, providing an additional source of tertiary alkyl radicals. Furthermore, quantum-chemical and master-equation calculations of the unimolecular decomposition of the primary alkyl radical reveal that isomerization to the tertiary alkyl radical is the most favorable pathway, and is favored over O2-addition at 650 K under the conditions herein. The isomerization pathway to tertiary alkyl radicals therefore contributes an additional mechanism to 2,2,5,5-tetramethyltetrahydrofuran formation; (3) carbonyl species (acetone, propanal, and methylpropanal) consistent with β-scission of QOOH radicals were formed in significant yield, indicating unimolecular QOOH decomposition into carbonyl + alkene + OH.

  9. Photoionization-photoelectron research

    SciTech Connect

    Berkowitz, J.; Ruscic, B.

    1993-12-01

    The photoionization research program is aimed at understanding the basic processes of interaction of vacuum ultraviolet (VUV) light with atoms and molecules. This research provides valuable information on both thermochemistry and dynamics. Recent studies include atoms, clusters, hydrides, sulfides and an important fluoride.

  10. Determining the partial photoionization cross-sections of ethyl radicals.

    PubMed

    FitzPatrick, B L; Maienschein-Cline, M; Butler, L J; Lee, S-H; Lin, J J

    2007-12-13

    Using a crossed laser-molecular beam scattering apparatus, these experiments photodissociate ethyl chloride at 193 nm and detect the Cl and ethyl products, resolved by their center-of-mass recoil velocities, with vacuum ultraviolet photoionization. The data determine the relative partial cross-sections for the photoionization of ethyl radicals to form C2H5+, C2H4+, and C2H3+ at 12.1 and 13.8 eV. The data also determine the internal energy distribution of the ethyl radical prior to photoionization, so we can assess the internal energy dependence of the photoionization cross-sections. The results show that the C2H4++H and C2H3++H2 dissociative photoionization cross-sections strongly depend on the photoionization energy. Calibrating the ethyl radical partial photoionization cross-sections relative to the bandwidth-averaged photoionization cross-section of Cl atoms near 13.8 eV allows us to use these data in conjunction with literature estimates of the Cl atom photoionization cross-sections to put the present bandwidth-averaged cross-sections on an absolute scale. The resulting bandwidth-averaged cross-section for the photoionization of ethyl radicals to C2H5+ near 13.8 eV is 8+/-2 Mb. Comparison of our 12.1 eV data with high-resolution ethyl radical photoionization spectra allows us to roughly put the high-resolution spectrum on the same absolute scale. Thus, one obtains the photoionization cross-section of ethyl radicals to C2H5+ from threshold to 12.1 eV. The data show that the onset of the C2H4++H dissociative photoionization channel is above 12.1 eV; this result offers a simple way to determine whether the signal observed in photoionization experiments on complex mixtures is due to ethyl radicals. We discuss an application of the results for resolving the product branching in the O+allyl bimolecular reaction.

  11. Biomedical applications of laser photoionization

    NASA Astrophysics Data System (ADS)

    Xiong, Xiaoxiong; Moore, Larry J.; Fassett, John R.; O'Haver, Thomas C.

    1991-07-01

    Trace elements are important for many essential metabolic functions. Zinc is a structural/functional component in more than 200 enzymes active in the biochemistry of cell division and tissue growth, neurology and endocrine control. Calcium is involved in intracellular control mechanisms and in skeletal bone building and resorption processes related to osteoporosis. Sensitive and selective laser photoionization is being developed to understand mechanisms in smaller samples and biological units approaching the cellular domain. Zinc has an ionization potential of 9.4 eV, or 75766.8 cm-1. Several processes are being explored, including two-photon resonant, three- photon ionization utilizing sequential UV transitions, e.g., 4s2 1S0 yields 4s4p 3P1 and 4s4p 3P1 yields 4s5d 3D1. Preliminary zinc stable isotope ratio data obtained by thermal atomization and laser photoionization agree with accepted values within 2 to 5%, except for anomalous 67Zn. Photoionization of calcium is being studied for isotope enrichment and ratio measurement using narrow and medium bandwidth lasers. Several ionization pathways, e.g., 4s2 1S0 - 2hv1 yields 4s10s - hv2 yields Ca+ (4s2S), are being investigated for isotopically selective ionization. Auto-ionization pathways are explored for greater efficiency in isotopic analysis. All studies have utilized a Nd:YAG- pumped laser system with one or two frequency-doubled tunable dye lasers coupled either to a magnetic sector or time-of-flight mass spectrometer.

  12. Photoionization and Dissociative Photoionization Study of Cholesterol by IR Laser Desorption/Tunable Synchrotron VUV Photoionization Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Pan, Yang; Zhang, Li-dong; Guo, Hui-jun; Yin, Hao; Qi, Fei

    2009-04-01

    Elementary cholesterol was analyzed with IR laser desorption/tunable synchrotron vacuum ultraviolet photoionization mass spectrometry. An exclusive molecular ion of cholesterol is observed by near threshold single-photon ionization with high efficiency. Fragments are yielded with the increase of photon energy. The structures of various fragments are determined with commercial electron ionization time-of-flight mass spectrometry. Dominant fragmentation pathways are discussed in detail with the aid of ab initio calculations.

  13. Indirect double photoionization of water

    NASA Astrophysics Data System (ADS)

    Resccigno, T. N.; Sann, H.; Orel, A. E.; Dörner, R.

    2011-05-01

    The vertical double ionization thresholds of small molecules generally lie above the dissociation limits corresponding to formation of two singly charged fragments. This gives the possibility of populating singly charged molecular ions by photoionization in the Franck-Condon region at energies below the lowest dication state, but above the dissociation limit into two singly charged fragment ions. This process can produce a superexcited neutral fragment that autoionizes at large internuclear separation. We study this process in water, where absorption of a photon produces an inner-shell excited state of H2O+ that fragments to H++OH*. The angular distribution of secondary electrons produced by OH* when it autoionizes produces a characteristic asymmetric pattern that reveals the distance, and therefore the time, at which the decay takes place. LBNL, Berkeley, CA, J. W. Goethe Universität, Frankfurt, Germany. Work performed under auspices of US DOE and supported by OBES, Div. of Chemical Sciences.

  14. Excitation energies, photoionization cross sections, and asymmetry parameters of the methyl and silyl radicals

    SciTech Connect

    Velasco, A. M.; Lavín, C.; Dolgounitcheva, O.; Ortiz, J. V.

    2014-08-21

    Vertical excitation energies of the methyl and silyl radicals were inferred from ab initio electron propagator calculations on the electron affinities of CH{sub 3}{sup +} and SiH{sub 3}{sup +}. Photoionization cross sections and angular distribution of photoelectrons for the outermost orbitals of both CH{sub 3} and SiH{sub 3} radicals have been obtained with the Molecular Quantum Defect Orbital method. The individual ionization cross sections corresponding to the Rydberg channels to which the excitation of the ground state's outermost electron gives rise are reported. Despite the relevance of methyl radical in atmospheric chemistry and combustion processes, only data for the photon energy range of 10–11 eV seem to be available. Good agreement has been found with experiment for photoionization cross section of this radical. To our knowledge, predictions of the above mentioned photoionization parameters on silyl radical are made here for the first time, and we are not aware of any reported experimental measurements. An analysis of our results reveals the presence of a Cooper minimum in the photoionization of the silyl radical. The adequacy of the two theoretical procedures employed in the present work is discussed.

  15. Nondipole effects in helium photoionization

    NASA Astrophysics Data System (ADS)

    Argenti, Luca; Moccia, Roberto

    2010-12-01

    An accurate calculation of the nondipole anisotropy parameter γ in the photoionization of helium below the N = 2 threshold is presented. The calculated results are in fairly good agreement with the experimental results of Krässig et al (2002 Phys. Rev. Lett. 88 203002), but not as good as the accuracy of the calculation should have warranted. A careful examination of the possible causes for the observed discrepancies between theory and experiment seems to rule out any role either of the multipolar terms higher than the electric quadrupole, or of the singlet-triplet spin-orbit mixing. It is argued that such discrepancies might have an instrumental origin, due to the difficulty of measuring vanishingly small total cross sections σtot with the required accuracy. In such eventuality, it might be more appropriate to use a parameter other than γ, such as for instance the drag current, to measure the nondipole anisotropy of the photoelectron angular distribution.

  16. Photoionization of rare gas clusters

    NASA Astrophysics Data System (ADS)

    Zhang, Huaizhen

    This thesis concentrates on the study of photoionization of van der Waals clusters with different cluster sizes. The goal of the experimental investigation is to understand the electronic structure of van der Waals clusters and the electronic dynamics. These studies are fundamental to understand the interaction between UV-X rays and clusters. The experiments were performed at the Advanced Light Source at Lawrence Berkeley National Laboratory. The experimental method employs angle-resolved time-of-flight photoelectron spectrometry, one of the most powerful methods for probing the electronic structure of atoms, molecules, clusters and solids. The van der Waals cluster photoionization studies are focused on probing the evolution of the photoelectron angular distribution parameter as a function of photon energy and cluster size. The angular distribution has been known to be a sensitive probe of the electronic structure in atoms and molecules. However, it has not been used in the case of van der Waals clusters. We carried out outer-valence levels, inner-valence levels and core-levels cluster photoionization experiments. Specifically, this work reports on the first quantitative measurements of the angular distribution parameters of rare gas clusters as a function of average cluster sizes. Our findings for xenon clusters is that the overall photon-energy-dependent behavior of the photoelectrons from the clusters is very similar to that of the corresponding free atoms. However, distinct differences in the angular distribution point at cluster-size-dependent effects were found. For krypton clusters, in the photon energy range where atomic photoelectrons have a high angular anisotropy, our measurements show considerably more isotropic angular distributions for the cluster photoelectrons, especially right above the 3d and 4p thresholds. For the valence electrons, a surprising difference between the two spin-orbit components was found. For argon clusters, we found that the

  17. Modeling X-Ray Photoionized Plasmas: Ion Storage Ring Measurements of Low Temperature Dielectronic Recombination Rate Coefficients for L-Shell Iron

    NASA Technical Reports Server (NTRS)

    Savin, D. W.; Badnell, N. R.; Bartsch, T.; Brandau, C.; Chen, M. H.; Grieser, M.; Gwinner, G.; Hoffknecht, A.; Kahn, S. M.; Linkemann, J.

    2000-01-01

    Iron L-shell ions (Fe XVII to Fe XXIV) play an important role in determining the line emission and thermal and ionization structures of photoionized gases. Existing uncertainties in the theoretical low temperature dielectronic recombination (DR) rate coefficients for these ions significantly affects our ability to model and interpret observations of photoionized plasmas. To help address this issue, we have initiated a laboratory program to produce reliable low temperature DR rates. Here, we present some of our recent results and discuss some of their astrophysical implications.

  18. Photoionization studies of oxygen and hydrogen

    NASA Astrophysics Data System (ADS)

    Padmanabhan, Arathi

    A toroidal spectrometer designed to perform (gamma, 2e) studies, was for the first time employed for Threshold Photoelectron Photoion Coincidence (TPEPICO) study. The angular distributions of O+(4S) ions produced from dissociative photoionization (DPI) of O2 + c4Sigma-u(nu =0,1) using the TPEPICO technique, i.e. by measuring the coincidence yield between threshold photoelectrons and photoions have been investigated. The results for lifetimes, taunu, corresponding to the vibrational levels nu = 0,1, along with the value obtained for inherent anisotropic photoion angular distribution betaO+, are presented. Recently, Fernandez and Martin (New J Phys 11 34 (2009)), have performed an extensive ab initio study of DPI in H2, in which large oscillatory behaviour in the electron angular distribution, as a function of electron energy, has been predicted. The result of their ab anitio calculations reveal that the electron angular, theta, distributions oscillate between a cos2theta pattern and isotropic with less than a 1 eV.change in electron energy. Due to the very low cross section and the requirement for high energy resolution in the electron detection system, these measurements require sensitive instrumentation that is now available at the Canadian Light Source. For this particular H 2 study, the electron angular distributions as a function of electron energy are the signature of quantum mechanical interference between, essentially, two specific doubly excited states (namely, 1Q11Sigma u+ and 1Q21piu) decaying at different internuclear distances. While interference between 'direct' photoionization and autoionization is well-known, the first unambiguous observation of interference between two autoionization processes, occurring on the femtosecond timescale is presented. A simple semi-classical model captures the essence of both our experimental observations and the results of full ab initio calculations. It does this through explicitly linking the electron angular

  19. Photoionization studies of (BH3)n (n=1,2)

    NASA Astrophysics Data System (ADS)

    Ruščić, B.; Mayhew, C. A.; Berkowitz, J.

    1988-05-01

    The results of photoionization mass spectrometric studies on B2H6, and BH3 (produced by pyrolysis of B2H6) are presented. The photoion yield curves of B2H+n (n=2-6) and BH+n (n=2-3) from B2H6, as well as BH+n (n=1-3) from BH3 have been obtained. It is shown that the combination of appearance potential measurements for BH+3 (B2H6) and BH+3 (BH3) yields a poor upper limit for -ΔHdimerization, 0 K (BH3) of 52.7 kcal/mol, while the combination of BH+2 (B2H6) and BH+2 (BH3) provides a better upper limit (46.6±0.6 kcal/mol) for this quantity. However, the threshold for BH+ (BH3), combined with auxiliary data, provides the best current experimental value, (34.3-39.1)±2 kcal/mol. This experimental value is in good agreement with a recent ab initio calculation, and is arrived at by using the best current estimate of ΔHf(B2H6), rather than a radically different value proposed in that paper. The ionization potential of BH3, ΔHf (BH+2), and the atomization energy of BH3 obtained experimentally are in excellent agreement with other ab initio calculations. The upper limits on heats of formation for the ionic species B2H+n (n=2-6) are obtained, and plausible structures are discussed for these species, based on the current energetics and various ab initio calculations. Finally, the fragmentation behavior of photoions from diborane is shown to have a more facile explanation by quasiequilibrium theory than by a molecular orbital picture, with the probable exception of BH+3 (B2H6).

  20. Photoionization of ClII

    NASA Astrophysics Data System (ADS)

    Nahar, Sultana; Hernández, E.; Antillón, A.; Morales, A.; González, O.; Macaluso, D.; Hanstorp, D.; Aguilar, A.; Juárez, A.; Hinojosa, G.

    2014-05-01

    The cross section and spectrum for the process of single photoionization of the chlorine cation was measured in the energy range of 19.5 to 28.0 eV with a photon energy resolution of 20 meV. Over a non resonant cross section, resonant structures originated from initinal Cl+ 3P(J=0,1,2) manifold converging mainly to 2P(J=3/2) and 2D(J=5/2) are identified. A theoretical calculation based on the close coupling R-matrix is under progress. CONACYT CB-2011 167631. US National Science Fundation, DGAPA IN106813, The ALS is supported by the Director, Office of Science, Office of Basic Energy Sciences, of the U.S. DOE Cntrct. DE-AC02-05CH11231. Montana Space Grant Consortium, Swedish Research Council.

  1. 2008 Photoions, Photoionization & Photodetachment Gordon Research Conference January 27-February 1, 2008

    SciTech Connect

    Klaus Muller-Dethefs Nancy Ryan GRay

    2009-03-31

    This conference brings together scientists interested in a range of basic phenomena linked to the ejection and scattering of electrons from atoms, molecules, clusters, liquids and solids by absorption of light. Photoionization, a highly sensitive probe of both structure and dynamics, can range from perturbative single-photon processes to strong-field highly non-perturbative interactions. It is responsible for the formation and destruction of molecules in astrophysical and plasma environments and successfully used in advanced analytical techniques. Positive ions, which can be produced and studied most effectively using photoionization, are the major components of all plasmas, vital constituents of flames and important intermediates in many chemical reactions. Negative ions are significant as transient species and, when photodetached, the corresponding neutral species often undergoes remarkable, otherwise non-observable, dynamics. The scope of the meeting spans from novel observations in atomic and molecular physics, such as Coulomb Crystals, highly excited states and cold Rydberg plasmas, to novel energy resolved or ultrafast time-resolved experiments, photoionization in strong laser fields, theoretical method development for electron scattering, photoionization and photodetachment and more complex phenomena such as charge transfer and DNA and protein conductivity, important for biological and analytical applications.

  2. An Atomic Photoionization Experiment by Harmonic Generation Spectroscopy

    NASA Astrophysics Data System (ADS)

    Trallero, Carlos; Frolov, Mikhail; Sarantseva, Tatiana S.; Manakov, Nikolay; Fulfer, Kristen D.; Wilson, Benjamin; Troß, Jan; Ren, Xiaoming; Poliakoff, Erwin; Silaev, Alexander A.; Vvedenskii, Nikolay; Starace, Anthony

    2016-05-01

    Measurements of the high-order harmonic generation yield of the argon (Ar) atom driven by a strong elliptically polarized laser field are shown to completely determine the field-free differential photoionization cross section of Ar, i.e., the energy dependence of both the angle-integrated photoionization cross section and the angular distribution asymmetry parameter. NSF EPSCoR Track II Nebraska-Kansas Awards No. 1430519 and No. 1430493.

  3. Photoionization in Collision Complexes

    DTIC Science & Technology

    1991-12-01

    neutrals were determined, kinetic energy distributions of fragment ions were measured, and the first reported analysis of clusters in a ternary...number densities of the neutrals can be determined. (7) Analysis of clusters in a ternary molecular beam has been carried out for the first time. (8...32 17 Energy Diagram for Neutral and Ionic Species in the CF3Br System 34 x LIST OF FIGURES (CONTINUED) Figure Title Page 18 Detailed Mass Spectra of 1

  4. A novel aerosol mass spectrometric approach - Analysis of the organic molecular signature of PM by coupling of thermal EC/OC-carbon analysis to photo-ionization mass spectrometry

    NASA Astrophysics Data System (ADS)

    Zimmermann, R.; Grabowski, J.; Streibel, T.; Sklorz, M.; Chow, J.

    2012-12-01

    Carbonaceous material in airborne particulate matter (PM) is of increasing interest e.g. due to its adverse health effects and its potential influence on the climate. Its analytical assessment on a molecular level is still very challenging. Hence, analysis of carbonaceous fractions for many studies is often solely carried out by determining sum parameters such as the overall content of organic carbon (OC) and elemental carbon (EC) as well as the total carbon content, TC (sum of OC and EC). The used thermal procedure, however, allows getting additional interesting information: By defining different thermal OC fractions (i.e. temperature steps) also information on the refractory properties of the carbonaceous material is obtained. In this context it is particularly interesting to investigate the release and formation behaviors of the molecular species responsible for the different OC and EC fractions. Thus after initial promising results of pre-studies [1,2] in the current work an EC/OC carbon analyzer (Model DRI 2000) and a homebuilt photo-ionization time-of-flight mass spectrometer (PI-TOFMS) were hyphenated and applied to investigate individual organic compounds especially from the different OC fractions. The carbon analyzer enables the stepwise heating of PM loaded filter samples and provides the sum values of the "carbon" release ("Improve protocol" [2]: OC1 - 120 °C, OC2 - 250°C, OC3 - 450°C OC4 - 550°C). With the on-line coupled PI-TOFMS evolved organic compounds, as released during the thermal program, are detectable in real time. This is possible by MS with soft photo ionization methods (SPI - single photon ionization and REMPI - resonance-enhanced multi photon ionization). Soft ionization suppresses fragmentation upon the ionization step and generates molecular signatures in the MS. The EC/OC-analyzer-PI-TOFMS instrument was applied to several types of PM samples, such as ambient aerosol, emission samples (gasoline/diesel car, wood combustion) or

  5. Photoionization-photoelectron research.

    SciTech Connect

    Ruscic, B.

    1998-03-06

    In the broad sense of a general definition, the fundamental goal of this research program is to explore, understand, and utilize the basic processes of interaction of vacuum UV light with atoms and molecules. In practical terms, this program uses photoionization mass spectrometry and other related techniques to study chemically relevant transient and metastable species that are intimately connected to energy-producing processes, such as combustion, or play-prominent roles in the associated environmental issues. Some recent examples of species that have been studied are: CH{sub 3}, CH{sub 2}, CH{sub 3}O, CH{sub 2}OH, CH{sub 3}S, CH{sub 2}SH, HCS, HNCO, NCO, HNCS, NCS, the isomers of C{sub 2}H{sub 5}O, HOBr, CF{sub 3} and CF{sub 3}OH. The ephemeral species of interest are produced in situ using various suitable techniques, such as sublimation, pyrolysis, microwave discharge, chemical abstraction reactions with H or F atoms, laser photodissociation, on-line synthesis, and others. The desired information is obtained by applying a variety of suitable photoionization methods, which use both conventional and coherent light sources in the vacuum W region. The spiritus movens of our studies is the need to provide the chemical community with essential information on the species of interest, such as accurate and reliable thermochemical, spectroscopic and structural data, and thus contribute to the global comprehension of the underlying chemical processes. The scientific motivation is also fueled by the necessity to unveil useful generalities, such as bonding patterns within a class of related compounds, or systematic behavior in the ubiquitous autoionization processes. In addition, the nature of the results obtained in this program is such that it generates a significant impetus for further theoretical work. The experimental work of this program is coordinated with other related experimental and theoretical efforts of the Chemical Dynamics Group to provide a broad perspective

  6. VUV photoionization cross sections of HO2, H2O2, and H2CO.

    PubMed

    Dodson, Leah G; Shen, Linhan; Savee, John D; Eddingsaas, Nathan C; Welz, Oliver; Taatjes, Craig A; Osborn, David L; Sander, Stanley P; Okumura, Mitchio

    2015-02-26

    The absolute vacuum ultraviolet (VUV) photoionization spectra of the hydroperoxyl radical (HO2), hydrogen peroxide (H2O2), and formaldehyde (H2CO) have been measured from their first ionization thresholds to 12.008 eV. HO2, H2O2, and H2CO were generated from the oxidation of methanol initiated by pulsed-laser-photolysis of Cl2 in a low-pressure slow flow reactor. Reactants, intermediates, and products were detected by time-resolved multiplexed synchrotron photoionization mass spectrometry. Absolute concentrations were obtained from the time-dependent photoion signals by modeling the kinetics of the methanol oxidation chemistry. Photoionization cross sections were determined at several photon energies relative to the cross section of methanol, which was in turn determined relative to that of propene. These measurements were used to place relative photoionization spectra of HO2, H2O2, and H2CO on an absolute scale, resulting in absolute photoionization spectra.

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

    PubMed

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

    2012-09-14

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

  8. Photoionization of P+: Experiment and theory

    NASA Astrophysics Data System (ADS)

    Nahar, S. N.; Hernández, E. M.; Hernández, L.; Antillón, A.; Morales-Mori, A.; González, O.; Covington, A. M.; Chartkunchand, K. C.; Hanstorp, D.; Juárez, A. M.; Hinojosa, G.

    2017-01-01

    An experimental and theoretical study of the single photoionization cross section of the P+ cation of phosphorus is presented. Photoionization (PI) cross sections are instrumental for the determination of abundances in the interstellar medium. The experiment was performed by merging an ion beam with a photon beam. The photon beam was nearly monochromatic and had an energy resolution of 24 meV. Calculations were carried out using the Breit-Pauli R-matrix method. The combined study was developed in the photon energy interval from 18 eV (68.9 nm) to 50 eV (24.8 nm). Comparison between the measured and the calculated cross section shows good agreement in general and identifies features of the process and existence of states in the experimental beam. The present results should provide for more accurate modeling of P+.

  9. Joint Measurements of Terahertz Wave Generation and High-Harmonic Generation from Aligned Nitrogen Molecules Reveal Angle-Resolved Molecular Structures

    NASA Astrophysics Data System (ADS)

    Huang, Yindong; Meng, Chao; Wang, Xiaowei; Lü, Zhihui; Zhang, Dongwen; Chen, Wenbo; Zhao, Jing; Yuan, Jianmin; Zhao, Zengxiu

    2015-09-01

    We report the synchronized measurements of terahertz wave generation and high-harmonic generation from aligned nitrogen molecules in dual-color laser fields. Both yields are found to be alignment dependent, showing the importance of molecular structures in the generation processes. By calibrating the angular ionization rates with the terahertz yields, we present a new way of retrieving the angular differential photoionization cross section (PICS) from the harmonic signals which avoids specific model calculations or separate measurements of the alignment-dependent ionization rates. The measured PICS is found to be consistent with theoretical predications, although some discrepancies exist. This all-optical method provides a new alternative for investigating molecular structures.

  10. Photoionization and photofragmentation of SF6 in helium nanodroplets.

    PubMed

    Peterka, Darcy S; Kim, Jeong Hyun; Wang, Chia C; Neumark, Daniel M

    2006-10-12

    The photoionization of He droplets doped with SF6 was investigated using tunable vacuum ultraviolet (VUV) synchrotron radiation from the Advanced Light Source (ALS). The resulting ionization and photofragmentation dynamics were characterized using time-of-flight mass spectrometry combined with photofragment and photoelectron imaging. Results are compared to those of gas-phase SF6 molecules. We find dissociative photoionization to SF5+ to be the dominant channel, in agreement with previous results. Key new findings are that (a) the photoelectron spectrum of the SF6 in the droplet is similar but not identical to that of the gas-phase species, (b) the SF5+ photofragment velocity distribution is considerably slower upon droplet photoionization, and (c) fragmentation to SF4+ and SF3+ is much less than in the photoionization of bare SF6. From these measurements we obtain new insights into the mechanism of SF6 photoionization within the droplet and the cooling of the hot photofragment ions produced by dissociative photoionization.

  11. Spectra of resonance surface photoionization

    SciTech Connect

    Antsiferov, V.V.; Smirnov, G.I.; Telegin, G.G.

    1995-09-01

    The theory of nonactivated electron transfer between atoms interacting reasonantly with coherent radiation and a metal surface is developed. The spectral resonances in photoabsorption and surface photoionization are found to be related to nonlinear interference effects in the interaction between discrete atomic levels and the continuum formed by the quasi-continuous electron spectrum of a normal metal. The asymmetry in the resonance surface photoionization spectrum is shown to have a shape typical of the Fano autoionization resonances. 18 refs.

  12. Inner-shell photoionization and core-hole decay of Xe and XeF2.

    PubMed

    Southworth, Stephen H; Wehlitz, Ralf; Picón, Antonio; Lehmann, C Stefan; Cheng, Lan; Stanton, John F

    2015-06-14

    Photoionization cross sections and partial ion yields of Xe and XeF2 from Xe 3d(5/2), Xe 3d(3/2), and F 1s subshells in the 660-740 eV range are compared to explore effects of the F ligands. The Xe 3d-ϵf continuum shape resonances dominate the photoionization cross sections of both the atom and molecule, but prominent resonances appear in the XeF2 cross section due to nominal excitation of Xe 3d and F 1s electrons to the lowest unoccupied molecular orbital (LUMO), a delocalized anti-bonding MO. Comparisons of the ion products from the atom and molecule following Xe 3d photoionization show that the charge-state distribution of Xe ions is shifted to lower charge states in the molecule along with production of energetic F(+) and F(2+) ions. This suggests that, in decay of a Xe 3d core hole, charge is redistributed to the F ligands and the system dissociates due to Coulomb repulsion. The ion products from excitation of the F 1s-LUMO resonance are different and show strong increases in the yields of Xe(+) and F(+) ions. The subshell ionization thresholds, the LUMO resonance energies, and their oscillator strengths are calculated by relativistic coupled-cluster methods and agree well with measurements.

  13. Physical mechanism of terahertz generation in two-color photoionization

    NASA Astrophysics Data System (ADS)

    You, Yong Sing

    Two-color photoionization has been widely used as a versatile tool for intense, broadband terahertz (THz) radiation generation. In this scheme, an ultrashort laser's fundamental and its second harmonic pulses are co-focused into a gas of atoms or molecules, transforming them into plasma by photoionization. This process produces an intense THz pulse emitted in the forward direction. The main focus of this dissertation is to provide a physical understanding of such THz generation and investigate its generation mechanism at both microscopic and macroscopic levels. First, we examine the generation process by measuring the relative phase between two-color (fundamental and second harmonic) laser fields and the resulting THz field simultaneously. We discover that a relative phase of pi/2 yields maximal THz outputs, consistent with a semi-classical plasma current model. We find that this optimal relative phase is independent of laser intensities, gas species, and two-color laser amplitude ratios. We also measure concurrent near-field photocurrents. All these measurements verify laser-produced plasma currents as a microscopic source for THz generation. We also investigate THz radiation from an ensemble of aligned air molecules in two-color laser fields. Our experiments show that THz radiation is strongly affected by molecular (nitrogen and oxygen) alignment. We explain this phenomenon in the context of the plasma current model combined with alignment-dependent ionization. Phase-matching is essential to achieve high-efficiency nonlinear frequency conversion. We discover THz generation by two-color photoionization in elongated air plasmas (filamentation) is naturally phase-matched in the off-axis direction, resulting in donut-shaped radiation profiles in the far field. Because of this off-axis phase-matching, THz yields increase almost linearly with the filament length, scalable for further THz energy enhancement. Lastly, we study the polarization of emitted THz radiation. In

  14. Quantitative measurement of radical intermediates by molecular-beam-sampling-mass-spectrometry

    SciTech Connect

    Chang, A.Y.; Dean, A.M.; Weisel, M.D.

    1995-03-01

    Complementary advances in theory and experiment have provided significant new insights into the complex chemistry occurring during high temperature pyrolysis and combustion. Detailed models have been developed for reactions in flames and engines as well as hydrocarbon pyrolysis. Such detailed models are generally considered to be more reliable if they can successfully describe the behavior of reactive intermediates, since these are usually much more sensitive to subtle details of the chemistry than either the reactants or products. In particular, accurate knowledge of the concentration-time profiles of these intermediates provide a rigorous test of the accuracy of the proposed kinetic model. The authors use a molecular-beam-sampling apparatus which utilizes both a vacuum ultraviolet photoionization time-of-flight spectrometer and an electron-impact quadrupole spectrometer to measure reactive intermediates as well as stable products of flow tube experiments.

  15. Photoionization research on atomic beams. 2: The photoionization cross section of atomic oxygen

    NASA Technical Reports Server (NTRS)

    Comes, F. J.; Speier, F.; Elzer, A.

    1982-01-01

    An experiment to determine the absolute value of the photo-ionization cross section of atomic oxygen is described. The atoms are produced in an electrical discharge in oxygen gas with 1% hydrogen added. In order to prevent recombination a crossed beam technique is employed. The ions formed are detected by a time-of-flight mass spectrometer. The concentration of oxygen atoms in the beam is 57%. The measured photoionization cross section of atomic oxygen is compared with theoretical data. The results show the participation of autoionization processes in ionization. The cross section at the autoionizing levels detected is considerably higher than the absorption due to the unperturbed continuum. Except for wavelengths where autoionization occurs, the measured ionization cross section is in fair agreement with theory. This holds up to 550 A whereas for shorter wavelengths the theoretical values are much higher.

  16. Vibrational branching ratios and shape resonant photoionization dynamics in N2O

    NASA Astrophysics Data System (ADS)

    Braunstein, M.; McKoy, V.

    1989-02-01

    Accurate photoelectron continuum orbitals are used to study vibrational branching ratios and photoelectron asymmetry parameters for alternative vibrational modes in the photoionization of N2O (7sigma exp -1). The strong non-Franck-Dondon vibrational ion distributions for the symmetric and antisymmetric stretching modes at low photoelectron energies observed in the dispersed ionic fluorescence measurements of Poliakoff et al. (1986) are confirmed. It is shown that these features arise from a sigma shape resonance which is associated with the molecular framework as a whole and not with either of its fragments, N-N or N-O.

  17. Measuring molecular weight by atomic force microscopy.

    PubMed

    Sheiko, Sergei S; da Silva, Marcelo; Shirvaniants, David; LaRue, Isaac; Prokhorova, Svetlana; Moeller, Martin; Beers, Kathryn; Matyjaszewski, Krzysztof

    2003-06-04

    Absolute-molecular-weight distribution of cylindrical brush molecules were determined using a combination of the Langmuir Blodget (LB) technique and Atomic Force Microscopy (AFM). The LB technique gives mass density of a monolayer, i.e., mass per unit area, whereas visualization of individual molecules by AFM enables accurate measurements of the molecular density, i.e., number of molecules per unit area. From the ratio of the mass density to the molecular density, one can determine the absolute value for the number average molecular weight. Assuming that the structure of brush molecules is uniform along the backbone, the length distribution should be virtually identical to the molecular weight distribution. Although we used only brush molecules for demonstration purpose, this approach can be applied for a large variety of molecular and colloidal species that can be visualized by a microscopic technique.

  18. Photoionization of Highly Charged Argon Ions and Their Diagnostic Lines

    NASA Astrophysics Data System (ADS)

    Nahar, Sultana N.

    2012-06-01

    %TEXT OF YOUR ABSTRACT Lines of highly charged He-like and Li-like ions in the ultraviolet and X-ray regions provide useful diagnostics for the physical and chemical conditions of the astrophysical as well as fusion plasmas. For example, Ar XVII lines in a Syfert galaxy have been measured by the X-ray space observatory Chandra. Results on photoionization of Ar XVI and Ar XVII obtained from relativistic Breit-Pauli R-matrix method and close-coupling approximation will be presented. Important features for level-specific photoionization for the diagnostic w, x, y, z lines of He-like Ar XVII in the ultraviolet region will be illustrated. Although monotonous decay dominates the low energy photoionization for these ions, strong resonances appear in the high energy region indicating higher recombination, inverse process of photoionization, at high temperature. The spectra of the well known 22 diagnostics dielectronic satellite lines of Li-like Ar XVI will be shown produced from the the KLL resonances in photoionization. Acknowledgement: Partially supported by DOE, NSF; Computational work was carried out at the Ohio Supercomputer Center

  19. Spin effects in double photoionization of lithium

    NASA Astrophysics Data System (ADS)

    Kheifets, A. S.; Fursa, D. V.; Hines, C. W.; Bray, I.; Colgan, J.; Pindzola, M. S.

    2010-02-01

    We apply the nonperturbative convergent close-coupling (CCC) and time-dependent close coupling (TDCC) formalisms to calculate fully differential energy and angular resolved cross sections of double photoionization (DPI) of lithium. The equal energy sharing case is considered in which dynamics of the DPI process can be adequately described by two symmetrized singlet and triplet amplitudes. The angular width of these amplitudes serves as a measure of the strength of the angular correlation between the two ejected electrons. This width is interpreted in terms of the spin of the photoelectron pair.

  20. Spin effects in double photoionization of lithium

    SciTech Connect

    Kheifets, A. S.; Fursa, D. V.; Hines, C. W.; Bray, I.; Colgan, J.; Pindzola, M. S.

    2010-02-15

    We apply the nonperturbative convergent close-coupling (CCC) and time-dependent close coupling (TDCC) formalisms to calculate fully differential energy and angular resolved cross sections of double photoionization (DPI) of lithium. The equal energy sharing case is considered in which dynamics of the DPI process can be adequately described by two symmetrized singlet and triplet amplitudes. The angular width of these amplitudes serves as a measure of the strength of the angular correlation between the two ejected electrons. This width is interpreted in terms of the spin of the photoelectron pair.

  1. Photoionization of epichlorohydrin enantiomers and clusters studied with circularly polarized vacuum ultraviolet radiation

    NASA Astrophysics Data System (ADS)

    Daly, Steven; Powis, Ivan; Garcia, Gustavo A.; Soldi-Lose, Héloïse; Nahon, Laurent

    2011-02-01

    The photoionization of enantiomerically pure epichlorohydrin (C3H5OCl) has been studied using linearly and circularly polarized vacuum ultraviolet synchrotron radiation. The threshold photoelectron spectrum was recorded and the first three bands assigned using molecular orbital calculations for the expected conformers, although uncertain experimental conformer populations and an anticipated breakdown in Koopmans' theorem leave some ambiguity. Measurements of the photoelectron circular dichroism (PECD) were obtained across a range of photon energies for each of these bands, using electron velocity map imaging to record the angular distributions, during which a record PECD chiral asymmetry factor of 32% was observed. A comparison with calculated PECD curves clarifies the assignment achieved using ionization energies alone and further suggests a likely relative population of the conformers. Threshold photoelectron-photoion coincidence methods were used to study the ionic fragmentation of epichlorohydrin. Fragment ion appearance energies show nonstatistical behavior with clear indications that the cationic epoxide ring is unstable and lower energy decay channels proceeding via ring breaking are generally open. Extensive neutral homochiral clusters of epichlorohydrin may be formed in supersonic molecular beam expansions seeded in Ar. Electron angular distribution measurements made in coincidence with dimer and trimer ions are used to effect an examination of the PECD associated with ionization of size-selected neutral cluster species, and these results differ clearly from PECD of the neutral monomer. The shifted ionization thresholds of the n-mers (n = 2, …, 7) are shown to follow a simple linear relationship, but under intense beam expansion conditions the monomer deviates from this relationship, and the monomer electron spectra tail to below the expected monomer adiabatic ionization potential (IP). PECD measurements made in coincidence with monomer ions obtained

  2. Photoionization of epichlorohydrin enantiomers and clusters studied with circularly polarized vacuum ultraviolet radiation.

    PubMed

    Daly, Steven; Powis, Ivan; Garcia, Gustavo A; Soldi-Lose, Héloïse; Nahon, Laurent

    2011-02-14

    The photoionization of enantiomerically pure epichlorohydrin (C(3)H(5)OCl) has been studied using linearly and circularly polarized vacuum ultraviolet synchrotron radiation. The threshold photoelectron spectrum was recorded and the first three bands assigned using molecular orbital calculations for the expected conformers, although uncertain experimental conformer populations and an anticipated breakdown in Koopmans' theorem leave some ambiguity. Measurements of the photoelectron circular dichroism (PECD) were obtained across a range of photon energies for each of these bands, using electron velocity map imaging to record the angular distributions, during which a record PECD chiral asymmetry factor of 32% was observed. A comparison with calculated PECD curves clarifies the assignment achieved using ionization energies alone and further suggests a likely relative population of the conformers. Threshold photoelectron-photoion coincidence methods were used to study the ionic fragmentation of epichlorohydrin. Fragment ion appearance energies show nonstatistical behavior with clear indications that the cationic epoxide ring is unstable and lower energy decay channels proceeding via ring breaking are generally open. Extensive neutral homochiral clusters of epichlorohydrin may be formed in supersonic molecular beam expansions seeded in Ar. Electron angular distribution measurements made in coincidence with dimer and trimer ions are used to effect an examination of the PECD associated with ionization of size-selected neutral cluster species, and these results differ clearly from PECD of the neutral monomer. The shifted ionization thresholds of the n-mers (n = 2, ..., 7) are shown to follow a simple linear relationship, but under intense beam expansion conditions the monomer deviates from this relationship, and the monomer electron spectra tail to below the expected monomer adiabatic ionization potential (IP). PECD measurements made in coincidence with monomer ions obtained

  3. Gas-Phase Photoionization Of A Protein

    NASA Astrophysics Data System (ADS)

    Milosavljevic, A. R.; Giuliani, A.; Nicolas, C.; Gil, J.-F.; Lemaire, J.; Refregiers, M.; Nahon, L.

    2010-07-01

    We present preliminary results on gas phase photoionization of electrosprayproduced multiply protonated cytochrome c protein (104 amino acids; ˜12.4 kDa), which has been achieved with a newly developed experimental system for spectroscopy of electrosprayed ions in a linear quadrupole ion trap using a monochromatized vacuum ultraviolet (VUV) synchrotron radiation and tandem mass spectrometry method. The investigation of proteins in the gas phase, where they are free of the influence of counterions and solvent molecules, offer a possibility to understand their intrinsic molecular properties. However, due to limited both ion densities and available number of photons, the use of synchrotron radiation for the trapped ions spectroscopy is a rather challenging task. The feasibility of coupling a Fourier transform ion cyclotron resonance ion trap with soft x-ray synchrotron beamline and the first successful use of synchrotron radiation for spectroscopy of electrosprayed negative ions stored in a three-dimensional quadrupole ion trap have been demonstrated only recently (R. Thissen et al., 2008, Phys. Rev. Lett., 100, 223001; A. Giulliani et al., Proc. 57th ASMS Conf., Philadelphia, 2009). The present results are the first reported on photoionization of kDa species in the gas phase and are valuable regarding both a fundamental interest of accessing physical properties of large biological ions isolated in vacuo and potential development of a new technique for proteomics.

  4. EUV optics in photoionization experiments

    NASA Astrophysics Data System (ADS)

    Bartnik, Andrzej; Wachulak, Przemysław; Fiedorowicz, Henryk; Fok, Tomasz; Jarocki, Roman; Kostecki, Jerzy; Szczurek, Anna; Szczurek, Mirosław; Pina, Ladislav; Sveda, Libor

    2013-05-01

    In this work photoionized plasmas were created by irradiation of He, Ne and Ar gases with a focused EUV beam from one of two laser-plasma sources employing Nd:YAG laser systems of different parameters. First of them was a 10-Hz laser-plasma EUV source, based on a double-stream gas-puff target, irradiated with the 3-ns/0.8J laser pulse. EUV radiation in this case was focused using a gold-plated grazing incidence ellipsoidal collector in the wavelength range λ = 9÷70 nm. The most intense emission was in the relatively narrow spectral region centred at λ = 11 +/- 1 nm. The second source was based on a 10 ns/10 J/10 Hz laser system. In this case EUV radiation was focused using a gold-plated grazing incidence multifoil collector or a Mo-coated ellipsoidal collector. The most intense emission in this case was in the 5 ÷ 15 nm spectral region. Radiation fluence ranged from 60 mJ/cm2 to 400 mJ/cm2. Different gases were injected into the interaction region, perpendicularly to an optical axis of the irradiation system, using an auxiliary gas puff valve. Irradiation of the gases resulted in ionization and excitation of atoms and ions. Spectra in EUV range were measured using a grazing incidence, flat-field spectrometer (McPherson Model 251), equipped with a 450 lines/mm toroidal grating. In all cases the most intense emission lines were assigned to singly charged ions. The other emission lines belong to atoms or doubly charged ions. The spectra were excited in low density gases of the order of 1 ÷ 10% atmospheric density.

  5. High-resolution soft x-ray photoionization studies of selected molecules

    SciTech Connect

    Hudson, Eric Allen

    1993-08-01

    Near-edge soft x-ray photoionization spectra were measured for CO, SF6, H2S, and D2S in the gas phase, using the Free University of Berlin plane-grating SX-700-II monochromator at the synchrotron radiation source BESSY. Photoionization spectra of carbon monoxide were measured near the carbon and oxygen K edges. Vibrational spacings and bond lengths are derived for several resonances. Results are consistent with equivalent-core model and indicate the different influences of the carbon and oxygen Is core holes. Corresponding spectra of H2CO and D2CO were also measured. Assignment of complex vibrational structure in valence-shell and Rydberg resonances is facilitated by comparison of spectra for the two isotopic species. Geometric and vibrational parameters are derived for several carbon 1s core-excited states. Isotopic shifts are observed in the energies and linewidths of some core-excited states. Sulfur hexafluoride photoionization spectra, measured near the sulfur L2,3 edges, show several series of weak, narrow Rydberg resonances. High resolution and good counting statistics allow a complete assignment of these states. Lineshapes of the broad inner-well resonances are analyzed to establish the magnitudes of vibrational and lifetime broadening in these states. Spectra of the H2S and D2S molecules were also measured near the sulfur L2,3 edges. Besides lower-energy transitions to inner-well states, a complex manifold of overlapping Rydberg resonances is observed. The rich fine structure of these states arises mainly from removal of orbital degeneracies in molecular field. Additional structure due to vibrational excitations in the final state is identified by comparison of the spectra for the two isotopic species.

  6. Photodetachment and photoionization rainbows and glories

    NASA Astrophysics Data System (ADS)

    Cohen, S.; Kalaitzis, P.; Danakas, S.; Lépine, F.; Bordas, C.

    2017-03-01

    Quantum scattering has many similarities with the physics of the atmospheric rainbow. Diffraction effects, including rainbows and glories, have long been introduced in the physics of scattering, and particularly in nuclear, atomic and molecular physics. In this paper we describe the striking similarity between the optics of the primary rainbow and supernumerary bows and photodetachment microscopy, with the latter term referring to the photodetachment of a structureless anion in the presence of a static electric field. Further, we extend the aforementioned analogy to the more complex and fertile case of photoionization microscopy. Despite the fact that in the latter situation the analogy is only approximate, we demonstrate the emergence of additional features that are also found in classical optics, like higher-order bows and glories. Finally, based on the conclusions drawn from the above analyses, we discuss the significant contribution of glories in threshold photoelectron spectroscopy.

  7. Double photoionization of tropone and cyclooctatetraene

    NASA Astrophysics Data System (ADS)

    Hartman, Tim; Wehlitz, Ralf

    2017-05-01

    We have studied the double-photoionization process of tropone (C7H6O) and cyclooctatetraene (C8H8) as a function of photon energy using monochromatized synchrotron radiation between 18 and 270 eV. We compare our results with previously published data for partially deuterated benzene (C6H3D3), which exhibits three distinct features in the ratio of doubly to singly charged parent ions, whereas pyrrole (C4H4N) exhibits only two of these features. The question that we address in this paper is how molecules with different molecular structures (pentagonal, hexagonal, heptagonal, and octagonal carbon rings) affect the photon-energy dependence of this ratio.

  8. Electronic properties and dissociative photoionization of thiocyanates. Part II. Valence and shallow-core (sulfur and chlorine 2p) regions of chloromethyl thiocyanate, CH2ClSCN.

    PubMed

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

    2012-01-12

    A combination of photoelectron spectroscopy and synchrotron based photoelectron photoion coincidence (PEPICO) spectra has been applied to investigate the electronic structure and the dissociative ionization of the CH(2)ClSCN molecule in the valence region. The PES is assigned with the electronic structure calculations at the outer-valence Green's function and symmetry adapted cluster/configuration interaction (SAC-CI) levels offer an explanation of our experimental results. Upon vacuum ultraviolet irradiation the low-lying radical cation, located at 10.39 eV is formed. The molecular ion is observed in the time-of-flight mass spectra, together with the CH(2)SCN(+) and CH(2)Cl(+) daughter ions. The total ion yield spectra have been measured in the S 2p and Cl 2p regions and several channels have been determined in dissociative photoionization events for the core-excited species. Thus, by using time-of-flight mass spectrometry and synchrotron radiation the relative abundances of the ionic fragments and their kinetic energy release values were obtained from both PEPICO and photoelectron photoion photoion coincidence spectra. Possible fragmentation processes are discussed and compared with that found for the related CH(3)SCN species.

  9. Double photoionization of doubly-excited lithium

    NASA Astrophysics Data System (ADS)

    Armstrong, G.; Pindzola, M. S.; Kheifets, A.; Schuricke, M.; Veeravalli, G.; Dornes, Ch.; Zhu, G.; Joachimsmeyer, K.; Treusch, R.; Dorn, A.; Colgan, J.

    2012-06-01

    We present triple differential cross sections and recoil ion momentum distributions for double photoionization of the 1s2s2p state of lithium. Double ionization of lithium may be treated as a two-active-electron process, where the ``active'' 2s and 2p electrons move in the field of the ``frozen-core'' Li^2+ 1s state.The time-dependent close-coupling (TDCC) method is used to solve the two-electron time-dependent Schr"odinger equation in full dimensionality. This work is motivated by recent FLASH experiments, which have obtained recoil-ion momentum distributions at a photon energy of 59 eV, where the 1s2s2p state is first reached via a 1s-2p photoexcitation from the initial ground state, and may then be doubly-ionized after the absorption of a second photon. The TDCC calculations in this work treat the subsequent photoionization of this doubly-excited state. The results are compared to those obtained by the convergent close-coupling method and to measurement, and provide a first comparison between theory and experiment in this fundamental few-photon few-body problem.

  10. Comparing Laser Desorption Ionization and Atmospheric Pressure Photoionization Coupled to Fourier Transform Ion Cyclotron Resonance Mass Spectrometry To Characterize Shale Oils at the Molecular Level

    USGS Publications Warehouse

    Cho, Yunjo; Jin, Jang Mi; Witt, Matthias; Birdwell, Justin E.; Na, Jeong-Geol; Roh, Nam-Sun; Kim, Sunghwan

    2013-01-01

    Laser desorption ionization (LDI) coupled to Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) was used to analyze shale oils. Previous work showed that LDI is a sensitive ionization technique for assessing aromatic nitrogen compounds, and oils generated from Green River Formation oil shales are well-documented as being rich in nitrogen. The data presented here demonstrate that LDI is effective in ionizing high-double-bond-equivalent (DBE) compounds and, therefore, is a suitable method for characterizing compounds with condensed structures. Additionally, LDI generates radical cations and protonated ions concurrently, the distribution of which depends upon the molecular structures and elemental compositions, and the basicity of compounds is closely related to the generation of protonated ions. This study demonstrates that LDI FT-ICR MS is an effective ionization technique for use in the study of shale oils at the molecular level. To the best of our knowledge, this is the first time that LDI FT-ICR MS has been applied to shale oils.

  11. Inner-shell photoionization and core-hole decay of Xe and XeF{sub 2}

    SciTech Connect

    Southworth, Stephen H.; Picón, Antonio; Lehmann, C. Stefan; Wehlitz, Ralf; Cheng, Lan; Stanton, John F.

    2015-06-14

    Photoionization cross sections and partial ion yields of Xe and XeF{sub 2} from Xe 3d{sub 5/2}, Xe 3d{sub 3/2}, and F 1s subshells in the 660–740 eV range are compared to explore effects of the F ligands. The Xe 3d-ϵf continuum shape resonances dominate the photoionization cross sections of both the atom and molecule, but prominent resonances appear in the XeF{sub 2} cross section due to nominal excitation of Xe 3d and F 1s electrons to the lowest unoccupied molecular orbital (LUMO), a delocalized anti-bonding MO. Comparisons of the ion products from the atom and molecule following Xe 3d photoionization show that the charge-state distribution of Xe ions is shifted to lower charge states in the molecule along with production of energetic F{sup +} and F{sup 2+} ions. This suggests that, in decay of a Xe 3d core hole, charge is redistributed to the F ligands and the system dissociates due to Coulomb repulsion. The ion products from excitation of the F 1s-LUMO resonance are different and show strong increases in the yields of Xe{sup +} and F{sup +} ions. The subshell ionization thresholds, the LUMO resonance energies, and their oscillator strengths are calculated by relativistic coupled-cluster methods and agree well with measurements.

  12. Single and double photoionization of beryllium below 40 eV

    SciTech Connect

    Wehlitz, R.; Bluett, J.B.; Lukic, D.

    2005-01-01

    We have measured the double-to-single photoionization ratio of beryllium (1s{sup 2}2s{sup 2}) between 28 and 40 eV and determined the relative single- and double-photoionization cross sections. In this energy region only simultaneous but not sequential emission of both 2s electrons can take place. We also compare our data with recent theoretical calculations and find good agreement with our data. The previously found scaling law for the double-to-single photoionization ratio is confirmed with high accuracy.

  13. IONIS: Approximate atomic photoionization intensities

    NASA Astrophysics Data System (ADS)

    Heinäsmäki, Sami

    2012-02-01

    A program to compute relative atomic photoionization cross sections is presented. The code applies the output of the multiconfiguration Dirac-Fock method for atoms in the single active electron scheme, by computing the overlap of the bound electron states in the initial and final states. The contribution from the single-particle ionization matrix elements is assumed to be the same for each final state. This method gives rather accurate relative ionization probabilities provided the single-electron ionization matrix elements do not depend strongly on energy in the region considered. The method is especially suited for open shell atoms where electronic correlation in the ionic states is large. Program summaryProgram title: IONIS Catalogue identifier: AEKK_v1_0 Program summary URL:http://cpc.cs.qub.ac.uk/summaries/AEKK_v1_0.html Program obtainable from: CPC Program Library, Queen's University, Belfast, N. Ireland Licensing provisions: Standard CPC licence, http://cpc.cs.qub.ac.uk/licence/licence.html No. of lines in distributed program, including test data, etc.: 1149 No. of bytes in distributed program, including test data, etc.: 12 877 Distribution format: tar.gz Programming language: Fortran 95 Computer: Workstations Operating system: GNU/Linux, Unix Classification: 2.2, 2.5 Nature of problem: Photoionization intensities for atoms. Solution method: The code applies the output of the multiconfiguration Dirac-Fock codes Grasp92 [1] or Grasp2K [2], to compute approximate photoionization intensities. The intensity is computed within the one-electron transition approximation and by assuming that the sum of the single-particle ionization probabilities is the same for all final ionic states. Restrictions: The program gives nonzero intensities for those transitions where only one electron is removed from the initial configuration(s). Shake-type many-electron transitions are not computed. The ionized shell must be closed in the initial state. Running time: Few seconds for a

  14. Photoionization Spectroscopy of Clusters

    NASA Astrophysics Data System (ADS)

    Dao, Phan Danh

    Studies of the electronic energies in van der Waals molecules (sometimes referred to as clusters or complexes) help one unravel the microscopic details of the condensed state. Furthermore, they provide the connection between gas-phase and condensed-phase sciences. To achieve this goal, we undertake (1) the spectroscopic studies of van der Waals complexes; (2) the determination of the ionization energies of van der Waals complexes, as well as of mixed alkali metal clusters (e.g., K(,n)O); and (3) the studies of processes that occur upon and after the ionization of van der Waals molecules (namely, dissociation and intracluster reactions). A brief discussion of the non-equilibrium synthesis of weakly bound molecules is given. The operation and performance of the pulsed supersonic jet are described along with some theoretical considerations. The characteristic features of the technique of laser ionization are presented with emphasis on its performance as a spectroscopic tool. Resonance two-photon ionization and time-of-flight mass spectrometry provide us with the tool to measure the perturbed electronic excited state of van der Waals complexes. In these studies, the chromophore species is an aromatic molecule having a single ring (phenylacetylene and para-xylene); and the "solvent" species are rare gas atoms, as well as a variey of molecules. In the case of chromophore-rare gas complexes, the S(,1) excited state is red-shifted, with respect to the nascent chromophore, and the magnitude of the shift shows a definite dependence on the atomic polarizability. Other salient trends of the measured spectral shifts are also discussed. In the measurement of complex ionization energies, the use of two tunable UV lasers is required. With p-xylene(.)Ar(,n) complexes (n = 1-6), these energies vary almost linearly with the number of atoms. Also discussed in the text are the effects of ionization in a weak DC field. A simple hydrogenic model of field-ionization is experimentally

  15. Pulsed-field ionization photoelectron and IR-UV resonant photoionization spectroscopy of Al-thymine.

    PubMed

    Krasnokutski, Serge A; Lei, Yuxiu; Lee, Jung Sup; Yang, Dong-Sheng

    2008-09-28

    Al-thymine (Al-C(4)H(3)N(2)O(2)CH(3)) is produced by laser vaporization of a rod made of Al and thymine powders in a molecular beam and studied by single-photon pulsed-field ionization-zero electron kinetic energy (ZEKE) photoelectron and IR-UV resonant two-photon ionization spectroscopy and density functional theory calculations. The ZEKE experiment determines the adiabatic ionization energy of the neutral complex and 22 vibrational modes for the corresponding ion with frequencies below 2000 cm(-1). The IR-UV photoionization experiment measures two N-H and three C-H stretches for the neutral species. The theoretical calculations predict a number of low-energy isomers with Al binding to single oxygen or adjacent oxygen and nitrogen atoms of thymine. Among these isomers, the structure with Al binding to the O4 atom of the diketo tautomer is predicted to be the most stable one by the theory and is probed by both ZEKE and IR-UV measurements. This work presents the first application of the IR-UV resonant ionization to metal-organic molecule systems. Like ZEKE spectroscopy, the IR-UV photoionization technique is sensitive for identifying isomeric structures of metal association complexes.

  16. Photoionization of methanol and formaldehyde

    NASA Technical Reports Server (NTRS)

    Warneck, P.

    1971-01-01

    Photoions produced in methanol and formaldehyde by radiation in the spectral region 450-1150 A were analyzed mass spectrometrically, and their relative yields were determined as a function of wavelength. First ionization potentials were determined, and the ion yield curves were interpreted in terms of ionization processes in conjunction with other data. Fragment ions were detected on mass numbers of 31, 30, 29, 15, and 14 for methanol, and 29, 2, and 1 for formaldehyde. The associated appearance potentials were determined and were used to calculate heats of formation of the ions CH2OH(+) and HCO(+), and the radicals CH3, CH2, and HCO.

  17. Photoionization of Isomeric Molecules: From the Weak-Field to the Strong-Field Limit

    NASA Astrophysics Data System (ADS)

    Zigo, Stefan John

    Ultra-fast spectroscopy has become a common tool for understanding the structure and dynamics of atoms and molecules, as evidenced by the award of the 1999 Nobel Prize in Chemistry to Ahmed H. Zewail for his pioneering work in femtochemistry. The use of shorter and more energetic laser pulses have given rise to high intensity table-top light sources in the visible and infrared which have pushed spectroscopic measurements of atomic and molecular systems into the strong-field limit. Within this limit, there are unique phenomena that are still not well understood. Many of such phenomena involve a photoionization step. For three decades, there has been a steady investigation of the single ionization of atomic systems in the strong-field regime both experimentally and theoretically. The investigation of the ionization of more complex molecular systems is of great interest presently and will help with the understanding of ultra-fast spectroscopy as a whole. In this thesis, we explore the single ionization of molecules in the presence of a strong electric field. In particular, we study molecular isomer pairs, molecules that are the same elementally, but different structurally. The main goal of this work is to compare the ionization yields of these similar molecular pairs as a function of intensity and gain some insight into what differences caused by their structure contribute to how they ionize in the strong-field limit. Through our studies we explore a wavelength dependence of the photoionization yield in order to move from the multi-photon regime of ionization to the tunneling regime with increasing wavelength. Also, in contrast to our strong-field studies, we investigate isomeric molecules in the weak-field limit through single photon absorption by measuring the total ionization yield as a function of photon energy. Our findings shed light on the complexities of photoionization in both the strong- and weak-field limits and will serve as examples for the continued

  18. Photoionization cross sections of the excited 3s3p 3Po state for atomic Mg

    NASA Astrophysics Data System (ADS)

    Wang, Guoli; Wan, Jianjie; Zhou, Xiaoxin

    2017-01-01

    The photoionization cross sections of the excited levels (3s3p 0,1,2,o 3P) of atomic Mg have been studied theoretically using both the nonrelativistic and fully relativistic R-matrix method. For the threshold cross sections, as previous nonrelativistic studies, present calculations show significant differences (a factor of 3) from former experimental values. Large discrepancies with experiment calls for additional measurements of the photoionization cross sections from the excited states of Mg.

  19. Global energy dependence of N2O+ >(A 2Σ+) photoion alignment

    NASA Astrophysics Data System (ADS)

    Das, Romith; Wu, Chuanyong; Poliakoff, E. D.

    1997-12-01

    We present experimental results for the alignment of N2O+(A 2Σ+) photoions over an extended energy range (16.4⩽hνexc⩽240 eV). The polarization of the N2O+(A 2Σ+→X 2Π) fluorescence is used to interpret the oscillator strength distributions for normally unresolved degenerate ionization channels. The results clearly show the influence of a near-threshold 7σ→kσ shape resonance, and help to clarify the results of previous fluorescence and photoelectron studies. At high photon energies, the photoelectrons are not favored to exit via a particular channel, in contrast to recent results on N2 and CO, where photoelectrons are ejected preferentially via the kσ channel and the photoions retain significant alignment even at the highest measurable energies. These results demonstrate that even well above threshold the spectral dependence of the alignment (i.e., polarization) is very sensitive to the molecular environment for photoejection.

  20. Photoionization studies of intramolecular dynamics: A closer look

    NASA Astrophysics Data System (ADS)

    Wu, Chuanyong

    Using synchrotron radiation as an excitation source, dispersed fluorescence measurements of two different molecular systems are presented in this dissertation with the intention to study the two fundamental aspects of shape resonances-complexity and completeness. C6F6 is a relative large and complex molecule in the sense that nonradiative transitions can take place unimolecularly in the free species. The elucidation of the ionization dynamics of this molecule helps to bridge the gap from simple molecules to matter in condensed phases. In the 2a2u-1 photoionization study of C6F6, the non-Franck-Condon behavior of the vibrational distributions at around 20 eV indicates the existence of shape resonances in this energy range. This is the first time a shape resonance of such a complex molecule is characterized with vibrational resolution detail over such a broad energy range. While the study of C6F6 is to disentangle the complexity aspect of shape resonance, the investigation of CO is an attempt to carry the shape resonant study to its completeness. The original goal of the 4σ- 1 photoionization study of CO was to investigate the vibrational-rotational-electronic (V-R-E) coupling. To be specific, we intended to study the shape resonant effects on the rotational population distributions for alternative vibrational levels. While the 4/sigma/to k/sigma shape resonance influences do not seem to be very significant, the results brought to attention another issue-continuum-continuum channel coupling. The study shows that the R-dependent aspects of shape- resonance-induced continuum coupling affects rotational population distributions for alternative vibrational states differently. In modern scientific researches, the development of instruments plays a critical role. The trend today is for computers to serve as the engine for instrumentation- virtual instruments. By walking through the development processes of a real-time instrument control and data acquisition system, the

  1. Measurement of the partial photoionization cross sections and asymmetry parameters of S atoms in the photon energy range 10.0-30.0 eV using constant-ionic-state spectroscopy

    SciTech Connect

    Innocenti, Fabrizio; Zuin, Lucia; Costa, Maria L.; Dias, Antonio A.; Morris, Alan; Stranges, Stefano; Dyke, John M.

    2007-04-21

    The partial photoionization cross sections and asymmetry parameters of S atoms have been measured using constant-ionic-state (CIS) spectroscopy in the photon energy range 10.0-30.0 eV. The ionizations investigated in these CIS experiments are the (3p){sup -1} ionizations S{sup +}({sup 4}S)(leftarrow)S({sup 3}P), S{sup +}({sup 2}D)(leftarrow)S({sup 3}P), and S{sup +}({sup 2}P)(leftarrow)S({sup 3}P). For the first time Rydberg series which converge to the fourth ionization limit have been observed and assignments of these series have been proposed. These correspond to excitations to Rydberg states that are parts of series which converge to the fourth ionization limit, S{sup +}({sup 4}P)(leftarrow)S({sup 3}P) (3s){sup -1}, and autoionize to the lower S{sup +}({sup 4}S), S{sup +}({sup 2}D), or S{sup +}({sup 2}P) states. For each series observed in the CIS spectra photoelectron angular distribution studies, combined with other evidence, has allowed the angular momentum character of the free electron on autoionization to be determined.

  2. State-To Dynamics of Photoionization and Charge Transfer Reactions Involving Hydrogen Bromide.

    NASA Astrophysics Data System (ADS)

    Xie, Jinchun

    The selection rules for electric-dipole-allowed photoionization of diatomic molecule are derived. From a single rotational level of neutral molecules, the final rotational levels of the ions can be accessed only when their angular momentum, parity, spin, and other quantum numbers satisfy certain relations concerning photoelectron partial waves. Furthermore, under irreducible tensor treatment photoionization probability is simply expressed by three factors: the geometrical coefficient C^ {k}_{p} the rotational linestrength S^{k}_{p } and the square of the tensor moment < {bf T}^{k} _{p}>. This method makes photoionization and electron impact induced transitions as easy to interpret as the well known multiphoton transition. The photoionization HBr^*(nu,J) + hnu to HBr ^+(^2Pi_{i},nu ^+,J^+) + e^- has been studied experimentally. The HBr^*(nu,J) is prepared in three 5ppi Rydberg states: f ^3Delta_2, g ^3Sigma^-_0 ^+ and F ^1Delta _2 via 2-photon excitation, and the product HBr^+(^2Pi_{i} ,nu^+,J^+ ) is probed in a quantum state specific manner using laser induced fluorescence (LIF). Distributions of the HBr^+ product show very strong parity propensities for the type of transition (+/- )-(mp), and also rotational propensities: Delta J = +/-1.5, +/-0.5 for the type of transition (+/-)-( mp) and Delta J = +/-2.5, +/-1.5, +/-0.5 for (+/-)-( +/-). These results are able to be described by using selection rules and irreducible moment presentation. The charge-transfer reaction DBr^+( ^2Pi_{i},nu^+,J ^+) + HBr to HBr ^+(^2Pi_{i^{ '}},nu^{'+ },J^{'+}) + DBr is studied under thermal conditions in a flowing gas mixture of HBr and DBr. The DBr^+(^2Pi _{i},nu^+,J^+) reagent is prepared by using (2 + 1) resonance enhanced multiphoton ionization and the HBr^+(^2 Pi_{i^{'+} },nu^{'+},J^ {'+}) product is detected using LIF. From the measurements of the molecular density and the populations of both HBr^+ and DBr^+, the absolute rate constants k(i,nu^+to i^', nu^{'+}) are determined for

  3. High-Resolution Photoelectron and Photoionization Spectroscopy

    NASA Astrophysics Data System (ADS)

    Merkt, F.

    2012-06-01

    Since its development in the late 1950s and early 1960s, photoelectron spectroscopy has established itself as an important method to study the electronic structure of molecules, their photoionization dynamics, and the structure and dynamics of molecular cations. In recent years, and particularly since the development of pulsed-field-ionization zero-kinetic-energy (PFI-ZEKE) photoelectron spectroscopy, considerable progress has been made in the resolution that can be achieved by photoelectron spectroscopy. This progress relies on the systematic exploitation of the unusual physical properties of high Rydberg states and enables one today to resolve the rotational structure in the photoelectron spectra of even large molecules and the hyperfine structure in the photoelectron spectra of small molecules. This talk will begin with a brief historical review of photoelectron spectroscopy. Then, the relationship between photoelectron spectroscopy, photoionization spectroscopy and the spectroscopy of high Rydberg states will be discussed. It will be explained how this relationship is currently exploited to improve the resolution achievable by PFI-ZEKE photoelectron spectroscopy. Then, the physical principles that are at the heart of the latest methods related to high-resolution photoelectron spectroscopy will be described together with their fundamental limitations. Depending on the resolution and the spectral range needed to address a specific scientific problem, a choice can be made between several different methods with spectral resolutions ranging from 30 GHz to better than 1 MHz. The talk will summarize the current state of the art in gas-phase photoelectron spectroscopy and be illustrated by several examples, primarily taken from the research in my group, in which photoelectron spectroscopy has contributed to answer questions concerning the structure and dynamics of small-sized molecular cations. F. I. Vilesov, B. C. Kurbatov, and N. Terrenin, Soviet Phys. (Doklady) 6

  4. VUV photoionization and dissociative photoionization spectroscopy of the interstellar molecule aminoacetonitrile: Theory and experiment

    NASA Astrophysics Data System (ADS)

    Bellili, A.; Schwell, M.; Bénilan, Y.; Fray, N.; Gazeau, M.-C.; Mogren Al-Mogren, M.; Guillemin, J.-C.; Poisson, L.; Hochlaf, M.

    2015-09-01

    Aminoacetonitrile (AAN) is a key compound in astrochemistry and astrobiology. We present a combined theoretical and experimental investigation concerning the single photoionization of gas-phase AAN and the fragmentation pathways of the resulting cation. At present, we measured photoelectron photoion coincidence (PEPICO) spectra in the 9.8-13.6 eV energy regime using synchrotron radiation as exciting light source. In order to interpret the VUV experimental data obtained, we explored the ground potential energy surface (PES) of AAN and of its cation using standard and explicitly correlated quantum chemical methodologies. This allowed us to deduce accurate thermochemical data for this molecule. We also determined, for the first time, the adiabatic ionization energy of AAN to lie at AIE = (10.085 ± 0.03) eV. The unimolecular decomposition pathways of the resulting AAN+ parent cation are also investigated. The appearance energies of five fragments are determined for the first time, with 30 meV accuracy. Interestingly, our work shows the possibility of the formation of both HCN and HNC isomeric forms. The implications for the evolution of prebiotic molecules under VUV irradiation are briefly discussed.

  5. Grating pitch measurements with the molecular measuring machine

    NASA Astrophysics Data System (ADS)

    Kramar, John; Jun, Jau-Shi J.; Penzes, William B.; Scire, Fredric; Teague, E. Clayton; Villarrubia, John S.

    1999-11-01

    At the National Institute of Standards and Technology, we are building a metrology instrument called the Molecular Measuring Machine (M3) with the goal of performing nanometer- accuracy two-dimensional feature placement measurements over a 50 mm by 50 mm area. The instrument uses a scanning tunneling microscope to probe the surface and an interferometer system to measure the lateral probe movement, both having sub-nanometer resolution. The continuous vertical measurement range is 5 micrometer, and up to 2 mm can be covered by stitching overlapping ranges. The instrument includes temperature control with millikelvin stability, an ultra-high vacuum environment with a base pressure below 10-5 Pa, and seismic and acoustic vibration isolation. Pitch measurements were performed on gratings made by holographic exposure of photoresist and on gratings made by laser-focused atomic deposition of Cr. The line pitch for these gratings ranged from 200 nm to 400 nm with an estimated standard uncertainty of the average pitch of 25 X 10-6. This fractional uncertainty is derived from an analysis of the sources of uncertainty for a 1 mm point-to- point measurement, including the effects of alignment, Abbe offset, motion cross-coupling, and temperature variations. These grating pitch measurements are uniquely accomplished on M3 because of the combination of probe resolution and long-range interferometer-controlled stage. This instrument could uniquely address certain dimensional metrology needs in the data storage industry.

  6. Precision Measurements with a Molecular Clock

    NASA Astrophysics Data System (ADS)

    Grier, Andrew; McDonald, Mickey; McGuyer, Bart; Iwata, Geoffrey; Apfelbeck, Florian; Tarallo, Marco; Zelevinsky, Tanya

    2015-05-01

    We report on recent results obtained with photoassociated Sr2 molecules confined in a lattice. Sr2 has a range of electronically excited bound states which are readily accessible with optical wavelengths using the narrow 1S0->3P1 intercombination line. As in Nat. Phys. 11, 32, we measure the lifetimes of the narrow, deeply-bound subradiant states in the 1g (1S0+3P1 dissociative limit) potential, allowing for coherent control of molecules and a comparison with theoretical predictions of the lifetimes and transition strengths of these states. Next, we study ultracold photodissociation of Sr2 molecules through abortion of one and two photons near the atomic intercombination line. This allows us to observe the vector character of transition elements through the angular dissociation pattern and to directly measure barrier heights in the excited state potentials. Finally, as shown in PRL 114, 023001, we demonstrate that in a non-magic lattice, a narrow transition can be used to measure the trapped gas temperature through the linewidth of the spectral feature corresponding to the carrier transitions. We use this technique to measure the temperature of Sr2 molecules to 10x higher precision than with standard techniques. We discuss future prospects with this molecular lattice clock. Funding from NIST, ARO, and NSF IGERT.

  7. Differential cross-sections for the double photoionization of lithium

    NASA Astrophysics Data System (ADS)

    Kheifets, A. S.; Fursa, D. V.; Bray, Igor; Colgan, J.; Pindzola, M. S.

    2012-11-01

    We apply the convergent close-coupling (CCC) and time-dependent close- coupling (TDCC) methods to describe energy and angular resolved double photoionization (DPI) of lithium at arbitrary energy sharing. By doing so, we are able to evaluate the recoil ion momentum distribution of DPI of Li and make a comparison with recent measurements of Zhu et al. [Phys. Rev. Lett. 103, 103008 (2009)].

  8. Differential cross sections of double photoionization of lithium

    SciTech Connect

    Kheifets, A. S.; Fursa, D. V.; Bray, I.; Colgan, J.; Pindzola, M. S.

    2010-08-15

    We extend our previous application of the convergent close-coupling (CCC) and time-dependent close-coupling (TDCC) methods [Phys. Rev. A 81, 023418 (2010)] to describe energy and angular resolved double photoionization (DPI) of lithium at arbitrary energy sharing. By doing so, we are able to evaluate the recoil ion momentum distribution of DPI of Li and make a comparison with recent measurements of Zhu et al. [Phys. Rev. Lett. 103, 103008 (2009)].

  9. Double photoionization of halogenated benzene

    SciTech Connect

    AlKhaldi, Mashaal Q.; Wehlitz, Ralf

    2016-01-28

    We have experimentally investigated the double-photoionization process in C{sub 6}BrF{sub 5} using monochromatized synchrotron radiation. We compare our results with previously published data for partially deuterated benzene (C{sub 6}H{sub 3}D{sub 3}) over a wide range of photon energies from threshold to 270 eV. A broad resonance in the ratio of doubly to singly charged parent ions at about 65 eV appears shifted in energy compared to benzene data. This shift is due to the difference in the bond lengths in two molecules. A simple model can explain the shape of this resonance. At higher photon energies, we observe another broad resonance that can be explained as a second harmonic of the first resonance.

  10. 2006 Photoions, Photoionization & Photodetachment held on January 29-February 3, 2006

    SciTech Connect

    Robert Continetti Nancy Ryan Gray

    2006-09-06

    The 4th Gordon Conference on Photoions, Photoionization and Photodetachment will be held January 29-February 3, 2006 at the Santa Ynez Valley Marriott in Buellton, California. This meeting will continue to cover fundamentals and applications of photoionization and photodetachment, including valence and core-level phenomena and applications to reaction dynamics, ultrashort laser pulses and the study of exotic molecules and anions. Further information will be available soon at the Gordon Conference Website, and will be announced.

  11. On the electron wavepacket dynamics of photoionizing states

    NASA Astrophysics Data System (ADS)

    Takatsuka, Kazuo

    2014-06-01

    To study electron wavepacket dynamics of photoionizing states in polyatomic molecules, we discuss two crucial issues to be overcome in the theory of molecular electronic wavepacket dynamics in an intense laser field (Takatsuka and Yonehara 2011 Phys. Chem. Chem. Phys. 13 4987). One is about the description of the ionization process from electronically excited states composed of many multiply excited configuration-state functions. The other is how to reconstruct the electronic states remaining in the molecular site while electrons are flowing out of the molecular bounds. These are both critical to extend the realm of the theories of electron dynamics based on the so-called expansion (algebraic) method in terms of basis functions. To calculate the photoionization amplitude and thereby to estimate the time-dependent amount of electron loss from a molecule, we extract the electron flux (probability current density) from the electron wavepackets without use of scattering theory. This is justified by the success of the recent works by Bandrauk’s group for attosecond photoionization dynamics from the hydrogen molecule ion, who performed numerical integration of the relevant Schrödinger equation (Yuan et al 2013 J. Chem. Phys. 138 134316). A key feature in the present study, on the other hand, is to calculate the electron flux in terms of complex-valued NOs, which arise from the complex electronic wavepackets. Through the change of these NOs, we reconstruct the involved electronic configurations during the flow of electrons out of molecular regions. These repopulated electronic wavefunctions are (non-adiabatically) evolved in time under laser fields.

  12. Photoelectron wave function in photoionization: Plane wave or Coulomb wave? [Does photoionization of neutral targets produce Coulomb or plane waves?

    DOE PAGES

    Gozem, Samer; Gunina, Anastasia O.; Ichino, Takatoshi; ...

    2015-10-28

    The calculation of absolute total cross sections requires accurate wave functions of the photoelectron and of the initial and final states of the system. The essential information contained in the latter two can be condensed into a Dyson orbital. We employ correlated Dyson orbitals and test approximate treatments of the photoelectron wave function, that is, plane and Coulomb waves, by comparing computed and experimental photoionization and photodetachment spectra. We find that in anions, a plane wave treatment of the photoelectron provides a good description of photodetachment spectra. For photoionization of neutral atoms or molecules with one heavy atom, the photoelectronmore » wave function must be treated as a Coulomb wave to account for the interaction of the photoelectron with the +1 charge of the ionized core. For larger molecules, the best agreement with experiment is often achieved by using a Coulomb wave with a partial (effective) charge smaller than unity. This likely derives from the fact that the effective charge at the centroid of the Dyson orbital, which serves as the origin of the spherical wave expansion, is smaller than the total charge of a polyatomic cation. Finally, the results suggest that accurate molecular photoionization cross sections can be computed with a modified central potential model that accounts for the nonspherical charge distribution of the core by adjusting the charge in the center of the expansion.« less

  13. Matched Molecular Series: Measuring SAR Similarity.

    PubMed

    Ehmki, Emanuel S R; Kramer, Christian

    2017-05-22

    Suggesting novel compounds to be made on the basis of similarity to a previously seen structure-activity relationship (SAR) requires a measure for SAR similarity. While SAR similarity has intuitively been used by medicinal chemists for decades, no systematic comparison of candidate similarity metrics has been published to date. With this publication, we attempt to close that gap by providing a statistical framework that allows comparison of SAR similarity metrics by their ability to rank series that provide the best activity prediction of novel substituents. This prediction is a result of a two-step process that involves (a) judging the similarity between series and (b) transferring the SAR from one series to the other. We tested several SAR similarity metrics and found that a centered RMSD (cRMSD) in combination with a lineaar-regression-based prediction interpolation ranks SAR profiles best. Based on that ranking we can, with a given confidence, suggest novel substituents to be tested. The superiority of the cRMSD can be explained on the basis of experimental uncertainty of affinity data and measured affinity differences. The ability to measure SAR similarity is central to applications like matched molecular series (MMS) analysis, whose applicability depends on whether there is a potential for SAR transferability between series. With the new SAR similarity metric introduced here, we show how MMS can be used in a medicinal chemistry setting as an idea generator and a semiquantitative prediction tool.

  14. Vibrationally resolved shape resonant photoionization of SiF4

    NASA Astrophysics Data System (ADS)

    Kakar, Sandeep; Poliakoff, E. D.; Rosenberg, R. A.

    1992-01-01

    We have measured vibrationally resolved fluorescence from SiF+4(D˜ 2A1) photoions to determine the vibrational branching ratio σ[v=(1,0,0,0)]/σ[v=(0,0,0,0)] in the excitation energy range 22photoionization are discussed.

  15. Band strength in photoelectron spectra and photoionization cross sections of pyrrole and of conformation isomers of 1,1-dimethylhydrazine

    SciTech Connect

    Kiro, Z. A.; Dykhanov, S. M.; Zverev, V. V.

    1988-09-01

    The dependence of partial photoionization cross sections of the 1,1-dimethylhydrazine molecule on the spatial characteristics (bond lengths, valence and dihedral angles) has been studied. The presence of a gauche-conformation isomer in the gaseous phase has been established, as confirmed by a comparison of the photoionization cross section ratios for the corresponding molecular orbitals with the relative band strengths in photoelectron spectra.

  16. An improved experimental scheme for simultaneous measurement of high-resolution zero electron kinetic energy (ZEKE) photoelectron and threshold photoion (MATI) spectra

    NASA Astrophysics Data System (ADS)

    Michels, François; Mazzoni, Federico; Becucci, Maurizio; Müller-Dethlefs, Klaus

    2017-10-01

    An improved detection scheme is presented for threshold ionization spectroscopy with simultaneous recording of the Zero Electron Kinetic Energy (ZEKE) and Mass Analysed Threshold Ionisation (MATI) signals. The objective is to obtain accurate dissociation energies for larger molecular clusters by simultaneously detecting the fragment and parent ion MATI signals with identical transmission. The scheme preserves an optimal ZEKE spectral resolution together with excellent separation of the spontaneous ion and MATI signals in the time-of-flight mass spectrum. The resulting improvement in sensitivity will allow for the determination of dissociation energies in clusters with substantial mass difference between parent and daughter ions.

  17. Relative partial cross sections for single, double, and triple photoionization of C60 and C70.

    PubMed

    Mitsuke, Koichiro; Katayanagi, Hideki; Kafle, Bhim P; Huang, Chaoqun; Yagi, Hajime; Prodhan, Md Serajul I; Kubozono, Yoshihiro

    2007-08-30

    Partial cross sections for the photoion formation from C(60) and C(70) were determined from the yields of singly, doubly, and triply charged ions which were measured by mass spectrometry combined with tunable synchrotron radiation at hnu = 25-120 eV. The dependence of the detection efficiencies on the mass-to-charge ratio was evaluated by using the formula proposed by Twerenbold et al. Corrections of the detection efficiency were found to be critical for obtaining accurate partial cross sections for photoionization of fullerenes. Revisions were made of the partial cross-section curves for single and double photoionization of C(60) and C(70). The curve for triple photoionization of C(70) was newly proposed. The ratios between the cross sections for double and single photoionization increase with hnu and reach saturated values of 0.78 at 85 eV for C(60) and approximately 1.3 at 100 eV for C(70). In contrast, the ratios at 120 eV between the cross sections for triple and single photoionization of C(60) and C(70) amount to 0.14 and approximately 0.38, respectively. The formation mechanism of multiply charged fullerene ions was discussed in terms of valence-electron excitation to antibonding unoccupied orbitals and/or spherical standing waves inside the cavity of a fullerene. This excitation could be followed by Spectator Auger processes and transmission of the excess electronic energy among numerous vibrational degrees of freedom.

  18. Photoionization sensors for non-invasive medical diagnostics

    NASA Astrophysics Data System (ADS)

    Mustafaev, Aleksandr; Rastvorova, Iuliia; Khobnya, Kristina; Podenko, Sofia

    2016-09-01

    The analysis of biomarkers can help to identify the significant number of diseases: lung cancer, tuberculosis, diabetes, high levels of stress, psychosomatic disorders etc. To implement continuous monitoring of the state of human health, compact VUV photoionization detector with current-voltage measurement is designed by Saint-Petersburg Mining University Plasma Research Group. This sensor is based on the patented method of stabilization of electric parameters - CES (Collisional Electron Spectroscopy). During the operation at atmospheric pressure VUV photoionization sensor measures the energy of electrons, produced in the ionization with the resonance photons, whose wavelength situated in the vacuum ultraviolet (VUV). A special software was developed to obtain the second-order derivative of the I-U characteristics, taken by the VUV sensor, to construct the energy spectra of the characteristic electrons. VUV photoionization detector has an unique set of parameters: small size (10*10*1 mm), low cost, wide range of recognizable molecules, as well as accuracy, sufficient for using this instrument for the medical purposes. This device can be used for non-invasive medical diagnostics without compromising the quality of life, for control of environment and human life. Work supported by Foundation for Assistance to Small Innovative Enterprises in Science and Technology.

  19. Acetylene/Vinylidene Isomerization after Carbon K-shell Photo-Ionization

    NASA Astrophysics Data System (ADS)

    Osipov, Timut; Weber, T.; Jahnke, T.; Alnaser, A.; Landers, A.; Hertlein, M.; Jagutzki, O.; Schmidt, L.; Schöffler, M.; Prior, M.; Feinberg, B.; Cocke, C. L.; Dörner, R.; Belkacem, A.

    2006-05-01

    Comprehensive study of the acetylene/vinylidene isomerization dynamics after the carbon k-shell photoionization followed by the Auger decay was performed by means of the COLTRIMS (COLd Target Recoil Ion Momentum Spectroscopy) technique. The Auger electrons, produced in this reaction, were detected in coincidence with the products of the Coulomb explosion of the dication C2H2^2+. Measurement of the 3d vector momenta for all detected particles inferred the Auger electron energies and directions in the body fixed molecular frame along with the KER (Kinetic Energy Release) for different break up channels. This highly differential reaction cross-section study provided very unique information about the fragmentation pathways of the doubly charged acetylene molecule.

  20. Absolute oscillator strengths for the valence and inner (P 2p,2s) shell photoabsorption, photoionization, and ionic photofragmentation of PF 3

    NASA Astrophysics Data System (ADS)

    Au, Jennifer W.; Brion, C. E.

    1997-08-01

    Absolute oscillator strengths (cross-sections) for the photoabsorption of phosphorus pentafluoride (PF 5) have been measured for the first time in the valence and phosphorus 2p discrete regions using high-resolution (0.0-0.1 eV fwhm), dipole ( e, e) spectroscopy. Long-range data (10-300 eV) have also been obtained at lower resolution (1 eV fwhm), from which the absolute oscillator strength scale has been determined using the valence-shell Thomas-Reiche-Kuhn sum-rule. The accuracy of the present measurement has been tested using the S(-2) sum rule normalization. Evaluation of the S(-2) sum using the presently reported absolute photoabsorption oscillator strength data gives a dipole polarizabilit for PF 5 in good agreement with the experimental value. The photoionization efficiencies, photoion branching ratios, and absolute partial oscillator strengths for molecular and dissociative photoionization have also been determined for PF 5 by dipole ( e, e+ion) coincidence spectroscopy from the first ionization threshold up to and above the phosphorus 2p edge.

  1. A discharge flow-photoionization mass spectrometric study of hydroxymethyl radicals (H{sub 2}COH and H{sub 2}COD): Photoionization spectrum and ionization energy

    SciTech Connect

    Tao, W.; Klemm, R.B.; Nesbitt, F.L.; Stief, L.J.

    1992-01-09

    The photoionization spectrum of H{sub 2}COH was measured over the wavelength range 140-170 nm by using a discharge flow-photoionization mass spectrometer apparatus with synchrotron radiation. Hydroxymethyl radicals (H{sub 2}COH and H{sub 2}COD) were generated in a flow tube by the reaction of F atoms with CH{sub 3}OH(D). Ionization energies (IE) were determined directly from photoion thresholds. The IE values, 7.56 {plus_minus} 0.02 and 7.55 {plus_minus} 0.02 eV for H{sub 2}COH and H{sub 2}COD, respectively, are consistent with previous measurements. Also, the dissociative ionization process, presumed to be H{sub 3}CO* {yields} HCO{sup +} + H{sub 2}, was observed with a threshold at 8.61 {plus_minus} 0.06 eV. 44 refs., 5 figs.

  2. Experimental observation of guanine tautomers with VUV photoionization

    SciTech Connect

    Zhou, Jia; Kostko, Oleg; Nicolas, Christophe; Tang, Xiaonan; Belau, Leonid; de Vries, Mattanjah S.; Ahmed, Musahid

    2008-12-01

    Two methods of preparing guanine in the gas phase, thermal vaporization and laser desorption, have been investigated. The guanine generated by each method is entrained in a molecular beam, single photon ionized with tunable VUV synchrotron radiation, and analyzed using reflectron mass spectrometry. The recorded photoionization efficiency (PIE) curves show a dramatic difference for experiments performed via thermal vaporization compared to laser desorption. The calculated vertical and adiabatic ionization energies for the eight lowest lying tautomers of guanine suggest the experimental observations arise from different tautomers being populated in the two different experimental methods.

  3. Mechanism of [m+h]+ formation in atmospheric pressure photoionization mass spectrometry: identification of propionitrile in acetonitrile with high mass accuracy measurement and tandem mass spectrometry and evidence for its involvement in the protonation phenomenon.

    PubMed

    Kamel, Amin; Jeanville, Patrick; Colizza, Kevin; J-Rivera, Lauren Elizabeth

    2008-11-01

    The role of propionitrile in the production of [M+H]+ under atmospheric pressure photoionization (APPI) was investigated. In dopant-assisted APPI using acetone and anisole, protonated acetone and anisole radical cations were the most prominent ions observed. In dopant-free or direct APPI in acetonitrile, however, a major ion in acetonitrile was detected and identified as propionitrile, using high accuracy mass measurement and collision induced dissociation studies. Vaporizing ca. 10(-5) M althiazide and bendroflumethazide under direct APPI in acetonitrile produced their corresponding protonated species [M+H]+. In addition to protonated acetonitrile, its dimers, and acetonitrile/water clusters, protonated propionitrile, propionitrile dimer, and propionitrile/water clusters were also observed. The role of propionitrile, an impurity in acetonitrile and/or a possible product of ion-molecule reaction, in the production of [M+H]+ of althiazide and bendroflumethazide was further investigated in the absence of dopant using propionitrile-d5. The formation of [M+D]+ species was observed, suggesting a possible role of propionitrile in the protonation process. Additionally, an increase in the [M+H]+ signal of althiazide and bendroflumethazide was observed as a function of propionitrile concentration in acetonitrile. Theoretical data from the literature supported the assumption that one possible mechanism, among others, for the formation of [M+H]+ could be attributed to photo-initiated isomerization of propionitrile. The most stable isomers of propionitrile, based on their calculated ionization energy (IE) and relative energy (DeltaE), were assumed to undergo proton transfer to the analytes, and mechanisms were proposed.

  4. 2s photoionization and subsequent Auger cascade in atomic Si

    SciTech Connect

    Partanen, L.; Fritzsche, S.; Jaenkaelae, K.; Huttula, M.; Osmekhin, S.; Aksela, H.; Aksela, S.; Urpelainen, S.

    2010-06-15

    The 2s photoionization and subsequent Auger transition cascade in atomic Si were studied by means of synchrotron-radiation-induced electron spectroscopy. After the 2s photoionization, the core hole states decay predominantly by a two-step Auger transition cascade into the triply ionized [Ne]nl states. The ionization channels of the 2s core-ionized Si{sup +} atoms to Si{sup 3+} ions were observed by measuring the conventional Auger electron spectra of the L{sub 1}-L{sub 2,3}M Coster-Kronig transitions and the L{sub 2,3}M-MMM Auger transitions. The observed L{sub 1}-L{sub 2,3}M and L{sub 2,3}M-MMM Auger spectra were analyzed by means of extensive multiconfiguration Dirac-Fock computations. We found that the electron correlation plays a prominent role in the Auger cascade, especially for the final-step Auger L{sub 2,3}M-MMM spectrum. Additionally, it was seen that the L{sub 2,3}M-MMM Auger spectrum of Si includes more Auger groups than the isoelectronic L{sub 2,3}-MM Auger spectrum of Al. Thus, more information on the intermediate ionic states is obtained if they are produced by Auger cascade rather than by direct photoionization.

  5. Excitons in Cuprous Oxide: Photoionization and Other Multiphoton Processes

    NASA Astrophysics Data System (ADS)

    Frazer, Nicholas Laszlo

    In cuprous oxide (Cu2O), momentum from the absorption of two infrared photons to make an orthoexciton is conserved and detected through the photon component of a resulting mixed exciton/photon (quadrupole exciton polariton) state. I demonstrated that this process, which actually makes the photon momentum more precisely defined, is disrupted by photoionization of excitons. Some processes are known to affect exciton propagation in both the pump and exciton stages, such as phonon emission, exciton-exciton (Auger) scattering, and third harmonic generation. These processes alone were not able to explain all observed losses of excitons or all detected scattering products, which lead me to design an optical pump-probe experiment to measure the exciton photoionization cross section, which is (3.9+/-0.2) x 10-22 m2. This dissertation describes the synthesis of cuprous oxide crystals using oxidation of copper, crystallization from melt with the optical floating zone method, and annealing. The cuprous oxide crystals were characterized using time and space resolved luminescence, leading to the discovery of new defect properties. Selection rules and overall efficiency of third harmonic generation in these crystals were characterized. Exciton photoionization was demonstrated through the depletion of polariton luminescence by an optical probe, the production of phonon linked luminescence as a scattering product, temporal delay of the probe, and time resolved luminescence. The results are integrated with the traditional dynamical model of exciton densities. An additional investigation of copper/cuprous oxide/gold photovoltaic devices is appended.

  6. 2001 Gordon Research Conference on Photoions, Photoionization and Photodetachment. Final progress report [agenda and attendees list

    SciTech Connect

    Johnson, Mark

    2001-07-13

    The Gordon Research Conference on Photoions, Photoionization and Photodetachment was held at Williams College, Williamstown, Massachusetts, July 8-13, 2001. The 72 conference attendees represented the spectrum of endeavor in this field, coming from academia, industry, and government laboratories, and including US and foreign scientists, senior researchers, young investigators, and students. Emphasis was placed on current unpublished research and discussion of the future target areas in this field. There was a conscious effort to stimulate discussion about the key issues in the field today. Time for formal presentations was limited. Sessions included the following topics: Vibrational structure, Time resolved studies: nuclear wavepackets, Valence photoionization, Clusters and networks, Resonance structures and decay mechanisms, Ultrafast photoionization, Threshold photoionization, Molecule fixed properties, and Collisional phenomena.

  7. Double Photoionization of Atomic Beryllium

    NASA Astrophysics Data System (ADS)

    Yip, Frank L.; McCurdy, C. William; Rescigno, Thomas N.

    2010-03-01

    One-photon double ionization (DPI) of beryllium represents the next step in the evolution of DPI investigations that began with helium in order to sensitively probe electron correlation. Beryllium is the simplest atomic species of the alkaline earth elements which, in general, possess two electrons outside of a fully occupied inner shell that spherically screens the nucleus. This provides a natural basis for comparison to 1s^2 helium DPI. However, the valence state of beryllium has n=2, thus making the valence excited target 2s2p more accessible relative to the 2s^2 ground state as compared to ground-state and metastable helium. Also, the symmetry of photoionizing from either the ^1S or ^1P initial state will have consequences for the angular distributions for double ionization. Triply differential cross sections (TDCS) are presented for DPI from both ground state 2s^2 and excited state 2s2p beryllium calculated using exterior complex scaling (ECS) for the valence electrons.

  8. A new method for direct total OH reactivity measurements using a fast Gas Chromatographic Photo-Ionization Detector (GC-PID)

    NASA Astrophysics Data System (ADS)

    Nölscher, A. C.; Sinha, V.; Bockisch, S.; Klüpfel, T.; Williams, J.

    2012-04-01

    The primary and most important oxidant in the troposphere is the hydroxyl radical (OH). Currently the atmospheric sinks of OH are poorly constrained. One way to characterize the overall sink term of OH is to measure directly the ambient loss rate of OH, the total OH reactivity. The first direct measurements of total OH reactivity were performed using laser induced fluorescence (LIF) [1], [2]. Recently a new method for determining OH reactivity was developed called the comparative reactivity method (CRM) [3]. The measurement principle is based on a competitive reaction between a reactive molecule not normally present in air with OH, and atmospheric OH reactive molecules with OH. The reactive molecule (X), is passed through a Teflon coated glass reactor and its concentration is monitored with a suitable detector. OH radicals are then introduced into the reactor at a constant rate to react with X, first in the presence of zero air and then in the presence of ambient air containing OH reactive species. Comparing the amount of X exiting the reactor with and without the competing ambient air molecules directly provides the atmospheric total OH reactivity. In the first version of this set up, molecule X is pyrrole (C5H4N) and the detector used is a proton transfer reaction mass spectrometer (PTR-MS). In comparison to the original LIF based system, the PTR-MS has the advantage of being smaller, less expensive, and commercially available. However, using the PTR-MS for total OH reactivity measurements prevents it from probing the broad variety of volatile organic compounds in ambient air. Moreover, even smaller, less expensive and more portable detectors are available. This work examines the potential for a GC-PID in order to make the total OH reactivity measurement accessible to more practitioners. This study presents measurements of total OH reactivity with a custom built GC-PID (VOC-Analyzer from IUT-Berlin, now ENIT (Environics-IUT GmbH))[4]. The GC-PID is small (260

  9. Extreme ultraviolet-induced photoionized plasmas

    NASA Astrophysics Data System (ADS)

    Bartnik, Andrzej; Wachulak, Przemyslaw; Fiedorowicz, Henryk; Fok, Tomasz; Jarocki, Roman; Szczurek, Miroslaw

    2014-05-01

    In this work photoionized plasmas were created by irradiation of He or Ne gases with a focused extreme ultraviolet (EUV) beam from one of two laser-plasma sources employing Nd:YAG laser systems. The first of them was a 10 Hz laser-plasma EUV source, based on a double-stream gas-puff target, irradiated with a 3 ns per 0.8 J laser pulse. EUV radiation in this case was focused using a gold-plated grazing incidence ellipsoidal collector. The second source was based on a 10 ns per 10 J per 10 Hz laser system. In this case EUV radiation was focused using a gold-plated grazing incidence multifoil collector. Gases were injected into the interaction region, perpendicularly to an optical axis of the irradiation system, using an auxiliary gas puff valve. Spectral measurements in the EUV range were performed. In all cases the most intense emission lines were assigned to singly charged ions. The other emission lines belong to atoms or doubly charged ions.

  10. Molecular approaches to measuring microbial marine pollution.

    PubMed

    Pommepuy, M; Le Guyader, F

    1998-06-01

    Developments in the rapid detection of pathogens (PCR and its variations) and molecular typing of strains isolated from the ecosystem illustrate the stimulation of research due to the recent foodborne and waterborne disease outbreaks.

  11. Photoionization from the 5p {sup 2}P{sub 3/2} state of rubidium

    SciTech Connect

    Nadeem, Ali; Haq, S. U.

    2011-06-15

    We report two-step photoionization studies from the 5p {sup 2}P{sub 3/2} excited state of rubidium using two dye lasers simultaneously pumped by a common Nd:YAG laser in conjunction with a thermionic diode ion detector. The photoionization cross section at the first ionization threshold is measured as 18.8 {+-} 3 Mb and at excess energies of 0.013, 0.106, 0.229, and 0.329 eV is measured as 15, 13.6, 12.6, and 12.5 Mb, respectively. The measured value of the photoionization cross section at the threshold is used to calibrate the oscillator strengths of the 5p {sup 2}P{sub 3/2}{yields}nd {sup 2}D{sub 5/2} (22 {<=}n{<=} 52) Rydberg transitions.

  12. Three-photon near-threshold photoionization dynamics of isooctane

    NASA Astrophysics Data System (ADS)

    Healy, Andrew T.; Underwood, David F.; Lipsky, Sanford; Blank, David A.

    2005-08-01

    The electron survival probability following three-photon (9.3eV total) near-threshold photoionization of neat isooctane is measured with sub-50fs time resolution. The measured dynamics are nonexponential in time and are well described by a diffusion-controlled electron-cation recombination model. Excitation-power-dependent studies indicate that the unperturbed three-photon threshold ionization is only observed for pump irradiance below 0.5TW/cm2. At excitation fields above this level, the signal is no longer cubic in the excitation irradiance, and the observed electron survival probability dramatically changes, decaying as a single exponential in time.

  13. Three-photon near-threshold photoionization dynamics of isooctane.

    PubMed

    Healy, Andrew T; Underwood, David F; Lipsky, Sanford; Blank, David A

    2005-08-01

    The electron survival probability following three-photon (9.3 eV total) near-threshold photoionization of neat isooctane is measured with sub-50 fs time resolution. The measured dynamics are nonexponential in time and are well described by a diffusion-controlled electron-cation recombination model. Excitation-power-dependent studies indicate that the unperturbed three-photon threshold ionization is only observed for pump irradiance below 0.5 TW cm2. At excitation fields above this level, the signal is no longer cubic in the excitation irradiance, and the observed electron survival probability dramatically changes, decaying as a single exponential in time.

  14. The photoionization spectrum of neutral aluminium, Al I

    NASA Technical Reports Server (NTRS)

    Roig, R. A.

    1975-01-01

    The absorption spectrum of Al I has been studied for the wavelength range 1160 to 2000 A by the flash pyrolysis technique. Wavelengths and derived energy levels are reported for 70 new lines converging on the 3s3p(3)P(0) limits of Al II. The autoionization parameters of the 3p(2)P(0)-3p(2)(2)S doublet have been measured. Good agreement is obtained with the experiment of Kohl and Parkinson and the recent calculation of Le Dourneuf et al. The relative photoionization cross section has been measured in the wavelength region 1200 A to 2000 A.

  15. Multichannel interactions in the resonant photoionization of HCl

    NASA Astrophysics Data System (ADS)

    White, M. G.; Leroi, G. E.; Ho, M.-H.; Poliakoff, E. D.

    1987-12-01

    Vibrational state distributions of the A 2Σ+ excited state of HCl+ were measured by dispersed fluorescence following resonant photoionization. Autoionization of levels excited at the NeI resonance line strongly influence the vibrational branching ratios of the A 2Σ+ state although not in accord with the propensity rule expected for vibrational autoionization. Other measurements utilizing total fluorescence yields and synchrotron radiation confirm the presence of competing dissociation channels for autoionizing Rydberg states converging to the A 2Σ+ limit. These results are discussed in terms of the multichannel interactions responsible for determining the observed ion and fragment product distributions.

  16. An experimental study of low-pressure premixed pyrrole/oxygen/argon flames with tunable synchrotron photoionization

    SciTech Connect

    Tian, Zhenyu; Li, Yuyang; Zhang, Taichang; Qi, Fei; Zhu, Aiguo; Cui, Zhifeng

    2007-10-15

    Two premixed laminar pyrrole/oxygen/argon flames at 3.33 kPa (25 Torr) with equivalence ratios of 0.55 (C/O/N = 1:5.19:0.25) and 1.84 (C/O/N = 1:1.56:0.25) have been investigated using tunable synchrotron photoionization and molecular-beam mass spectrometry techniques. All observed flame species, including some nitrogen-containing intermediates, have been identified by measurements of photoionization efficiency spectra. Mole fraction profiles of species including reactants, intermediates, and products have been determined by scanning burner position at some selected photon energies near ionization thresholds, and flame temperature has been measured by a Pt/Pt-13% Rh thermocouple. The results indicate that N{sub 2}, NO, and NO{sub 2} are the major nitrogenous products, while hydrogen cyanide, isocyanic acid, and 2-propenenitrile are the most important nitrogen-containing intermediates in pyrrole flames. Radicals such as methyl, propargyl, allyl, cyanomethyl, n-propyl, isobutyl, cyclopentadienyl, phenyl, cyclohexyl, phenoxy, and 4-methylbenzyl are observed as well. Moreover, ethenol and methylacrylonitrile are also detected. Reaction pathways involving the major species are proposed. The new results will be useful in developing a kinetic model of nitrogenous compound combustion. (author)

  17. Photo-ionization rate coefficients for the rare gases

    NASA Astrophysics Data System (ADS)

    Pang, Xuexia

    2005-01-01

    By introducing the converting method from electron-impact ionization cross sections to rate coefficients through using a semi-experiential formula, we try to probe a semi-experiential formula for converting the photo-ionization cross sections into photo-ionization rate coefficient. It"s found that photo-ionization rate coefficient is direct proportion to photo-ionization cross sections, the rate S is related with light resource.

  18. A discharge flow-photoionization mass spectrometric study of the FO(X 2 Pi i) radical. Photoionization efficiency spectrum and ionization energy

    NASA Technical Reports Server (NTRS)

    Zhang, Zhengyu; Kuo, Szu-Cherng; Klemm, R. Bruce; Monks, Paul S.; Stief, Louis J.

    1994-01-01

    Photoionization efficiency spectra of FO were measured over the wavelength range 80.0-100.0 nm and in the ionization threshold region, 94.0-100.0 nm, using a discharge flow-photoionization mass spectrometer apparatus coupled to a synchrotron radiation source. FO was generated by the reaction of F2P atoms with NO3 and via a F2O2 discharge. A value of 12.78 +/- 0.03 eV was obtained for the adiabatic ionization energy of FO from photoion thresholds which corresponds to FO(+)(X 3 Sigma -) from FO(X 2 Pi i). These results, which are the first to be obtained by direct Photo-ionization mass spectrometry (PIMS) measurements, corroborate those of a photoelectron spectroscopy (PES) study; however, the ionization energy determined here is free from interferences due to other species which complicated the PES measurement. A value of 109.5 +/- 8.0 kJ/mol for Delta f H 0 298(FO) is computed from the present value of IE(FO) and a previous appearance energy measurement, and a value for the proton affinity of FO is calculated to be 511.5 +/- 10.0 kJ/mol.

  19. A discharge flow-photoionization mass spectrometric study of the FO(X 2 Pi i) radical. Photoionization efficiency spectrum and ionization energy

    NASA Technical Reports Server (NTRS)

    Zhang, Zhengyu; Kuo, Szu-Cherng; Klemm, R. Bruce; Monks, Paul S.; Stief, Louis J.

    1994-01-01

    Photoionization efficiency spectra of FO were measured over the wavelength range 80.0-100.0 nm and in the ionization threshold region, 94.0-100.0 nm, using a discharge flow-photoionization mass spectrometer apparatus coupled to a synchrotron radiation source. FO was generated by the reaction of F2P atoms with NO3 and via a F2O2 discharge. A value of 12.78 +/- 0.03 eV was obtained for the adiabatic ionization energy of FO from photoion thresholds which corresponds to FO(+)(X 3 Sigma -) from FO(X 2 Pi i). These results, which are the first to be obtained by direct Photo-ionization mass spectrometry (PIMS) measurements, corroborate those of a photoelectron spectroscopy (PES) study; however, the ionization energy determined here is free from interferences due to other species which complicated the PES measurement. A value of 109.5 +/- 8.0 kJ/mol for Delta f H 0 298(FO) is computed from the present value of IE(FO) and a previous appearance energy measurement, and a value for the proton affinity of FO is calculated to be 511.5 +/- 10.0 kJ/mol.

  20. Double photoionization of hydrocarbons and aromatic molecules

    NASA Astrophysics Data System (ADS)

    Wehlitz, R.

    2016-11-01

    This article reviews the recent progress in the field of double photoionization of hydrocarbons and aromatic molecules using synchrotron radiation. First I will describe the importance of carbon-based molecules, which are all around us and are literally part of our life. They exhibit intriguing properties some of which can be probed via double photoionization, i.e., the simultaneous emission of two electrons. Furthermore, I will discuss the different mechanisms that can lead to a doubly charged organic molecule and will highlight those findings by comparing them with the results for atoms and other (simple) molecules. Finally, I will give an outlook on future directions on this subject.

  1. Absolute photoionization cross sections of furanic fuels: 2-ethylfuran, 2-acetylfuran and furfural.

    PubMed

    Smith, Audrey R; Meloni, Giovanni

    2015-11-01

    Absolute photoionization cross sections of the molecules 2-ethylfuran, 2-acetylfuran and furfural, including partial ionization cross sections for the dissociative ionized fragments, are measured for the first time. These measurements are important because they allow fuel quantification via photoionization mass spectrometry and the development of quantitative kinetic modeling for the complex combustion of potential fuels. The experiments are carried out using synchrotron photoionization mass spectrometry with an orthogonal time-of-flight spectrometer used for mass analysis at the Advanced Light Source of Lawrence Berkeley National Laboratory. The CBS-QB3 calculations of adiabatic ionization energies and appearance energies agree well with the experimental results. Several bond dissociation energies are also derived and presented.

  2. Photoionization of Doubly-Charged Ba2+ Ions using an ECR Ion Source and Synchrotron Radiation

    NASA Astrophysics Data System (ADS)

    Bizau, J.-M.; Esteva, J. M.; Cubaynes, D.; Wuilleumier, F. J.; Petrault, L.; Marmoret, R.; Couillaud, C.; Compant La Fontaine, A.; Blancard, C.; Hitz, D.; Ludwig, P.; Morgan, T. J.

    2000-06-01

    Following our first photoionization measurements [1] along the isonuclear series of multiply-charged xenon ions performed using synchrotron radiation and an ECR ion source, we introduced several modifications in the experimental set-up to allow the production of multiply-charged ions of metals. With a resistively-heated oven and a new Wien-filter, we are now able to produce a few hundred nananoamperes up to Ba5+ ions. The first photoionization spectra for photoionization of Ba2+ have been recently measured, in good agreement with earlier results of Kennedy et al. obtained in dual laser experiments [2]. The characteristics of our new experimental device will be described and the preliminary results will be presented. 1. J-M. Bizau et al., Phys. Rev. Lett. 84, 435 (2000). 2. E. T. Kennedy et al., J. Electr. Spectr. 79, 283( 1996).

  3. Benchmark Experiment for Photoionized Plasma Emission from Accretion-Powered X-Ray Sources

    NASA Astrophysics Data System (ADS)

    Loisel, G. P.; Bailey, J. E.; Liedahl, D. A.; Fontes, C. J.; Kallman, T. R.; Nagayama, T.; Hansen, S. B.; Rochau, G. A.; Mancini, R. C.; Lee, R. W.

    2017-08-01

    The interpretation of x-ray spectra emerging from x-ray binaries and active galactic nuclei accreted plasmas relies on complex physical models for radiation generation and transport in photoionized plasmas. These models have not been sufficiently experimentally validated. We have developed a highly reproducible benchmark experiment to study spectrum formation from a photoionized silicon plasma in a regime comparable to astrophysical plasmas. Ionization predictions are higher than inferred from measured absorption spectra. Self-emission measured at adjustable column densities tests radiation transport effects, demonstrating that the resonant Auger destruction assumption used to interpret black hole accretion spectra is inaccurate.

  4. Double-to-single photoionization ratio of lithium at medium energies

    SciTech Connect

    Wehlitz, R.; Bluett, J.B.; Martinez, M.M.; Lukic, D.; Whitfield, S.B.

    2004-06-01

    The double-to-single photoionization ratio of atomic lithium has been measured for photon energies ranging from 120 eV to 910 eV. Through extensive use of various filters we were able to significantly extend the previous range of measurements [M.-T. Huang et al., Phys. Rev. A 59, 3397 (1999)]. We find that our data are in agreement with the predicted high-energy limit of 3.4%. By applying simple model curves to our data, we believe that sequential processes contribute substantially to the double-photoionization cross-section ratio as predicted by theory.

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

    SciTech Connect

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

    2012-09-14

    We have developed an ion-molecule reaction apparatus for state-selected absolute total cross section measurements by implementing a high-resolution molecular beam vacuum ultraviolet (VUV) laser pulsed field ionization-photoion (PFI-PI) ion source to a double-quadrupole double-octopole ion-guide mass spectrometer. Using the total cross section measurement of the state-selected N{sub 2}{sup +}(v{sup +}, N{sup +}) + Ar charge transfer (CT) reaction as an example, we describe in detail the design of the VUV laser PFI-PI ion source used, which has made possible the preparation of reactant N{sub 2}{sup +}(X {sup 2}{Sigma}{sub g}{sup +}, v{sup +}= 0-2, N{sup +}= 0-9) PFI-PIs with high quantum state purity, high intensity, and high kinetic energy resolution. The PFI-PIs and prompt ions produced in the ion source are shown to have different kinetic energies, allowing the clean rejection of prompt ions from the PFI-PI beam by applying a retarding potential barrier upstream of the PFI-PI source. By optimizing the width and amplitude of the pulsed electric fields employed to the VUV-PFI-PI source, we show that the reactant N{sub 2}{sup +} PFI-PI beam can be formed with a laboratory kinetic energy resolution of {Delta}E{sub lab}={+-} 50 meV. As a result, the total cross section measurement can be conducted at center-of-mass kinetic energies (E{sub cm}'s) down to thermal energies. Absolute total rovibrationally selected cross sections {sigma}(v{sup +}= 0-2, N{sup +}= 0-9) for the N{sub 2}{sup +}(X {sup 2}{Sigma}{sub g}{sup +}; v{sup +}= 0-2, N{sup +}= 0-9) + Ar CT reaction have been measured in the E{sub cm} range of 0.04-10.0 eV, revealing strong vibrational enhancements and E{sub cm}-dependencies of {sigma}(v{sup +}= 0-2, N{sup +}= 0-9). The thermochemical threshold at E{sub cm}= 0.179 eV for the formation of Ar{sup +} from N{sub 2}{sup +}(X; v{sup +}= 0, N{sup +}) + Ar was observed by the measured {sigma}(v{sup +}= 0), confirming the narrow {Delta}E{sub cm} spread achieved in

  6. Measuring the mechanical properties of molecular conformers

    NASA Astrophysics Data System (ADS)

    Jarvis, S. P.; Taylor, S.; Baran, J. D.; Champness, N. R.; Larsson, J. A.; Moriarty, P.

    2015-09-01

    Scanning probe-actuated single molecule manipulation has proven to be an exceptionally powerful tool for the systematic atomic-scale interrogation of molecular adsorbates. To date, however, the extent to which molecular conformation affects the force required to push or pull a single molecule has not been explored. Here we probe the mechanochemical response of two tetra(4-bromophenyl)porphyrin conformers using non-contact atomic force microscopy where we find a large difference between the lateral forces required for manipulation. Remarkably, despite sharing very similar adsorption characteristics, variations in the potential energy surface are capable of prohibiting probe-induced positioning of one conformer, while simultaneously permitting manipulation of the alternative conformational form. Our results are interpreted in the context of dispersion-corrected density functional theory calculations which reveal significant differences in the diffusion barriers for each conformer. These results demonstrate that conformational variation significantly modifies the mechanical response of even simple porpyhrins, potentially affecting many other flexible molecules.

  7. Measuring the mechanical properties of molecular conformers.

    PubMed

    Jarvis, S P; Taylor, S; Baran, J D; Champness, N R; Larsson, J A; Moriarty, P

    2015-09-21

    Scanning probe-actuated single molecule manipulation has proven to be an exceptionally powerful tool for the systematic atomic-scale interrogation of molecular adsorbates. To date, however, the extent to which molecular conformation affects the force required to push or pull a single molecule has not been explored. Here we probe the mechanochemical response of two tetra(4-bromophenyl)porphyrin conformers using non-contact atomic force microscopy where we find a large difference between the lateral forces required for manipulation. Remarkably, despite sharing very similar adsorption characteristics, variations in the potential energy surface are capable of prohibiting probe-induced positioning of one conformer, while simultaneously permitting manipulation of the alternative conformational form. Our results are interpreted in the context of dispersion-corrected density functional theory calculations which reveal significant differences in the diffusion barriers for each conformer. These results demonstrate that conformational variation significantly modifies the mechanical response of even simple porpyhrins, potentially affecting many other flexible molecules.

  8. Correlation between photoeletron and photoion in ultrafast multichannel photoionization of Ar

    SciTech Connect

    Itakura, R.; Fushitani, M.; Hishikawa, A.; Sako, T.

    2015-12-31

    We theoretically investigate coherent dynamics of ions created through ultrafast multichannel photoionization from a viewpoint of photoelectron-photoion correlation. The model calculation on single-photon ionization of Ar reveals that the coherent hole dynamics in Ar{sup +} associated with a superposition of the spin-orbit states {sup 2}PJ (J = 3/2 and 1/2) can be identified by monitoring only the photoion created by a Fourier-transform limited extreme ultraviolet (EUV) pulse with the fs pulse duration, while the coherence is lost by a chirped EUV pulse. It is demonstrated that by coincidence detection of the photoelectron and photoion the coherent hole dynamics can be extracted even in the case of ionization by a chirped EUV pulse with the sufficiently wide bandwidth.

  9. Laser flash photolysis study of photoionization in fluoroquinolones.

    PubMed

    Monti, Sandra; Sortino, Salvatore

    2002-11-01

    A laser flash photolysis investigation was carried out on the mechanism of electron photoejection in fluoroquinolone derivatives, bearing either electron donating or electron accepting substituents in position 8, laser excited at lambda(exc) = 355 nm in neutral aqueous solutions. The dependence of the hydrated electron absorption at 720 nm on the laser intensity and on the presence of N2O as electron scavenger evidenced that in enoxacin, norfloxacin, and lomefloxacin the photoionization is predominantly two-photon. With rufloxacin, besides the two-photon process, a one photon contribution with a quantum yield of 0.034 was measured.

  10. Differential cross sections of double photoionization of lithium

    NASA Astrophysics Data System (ADS)

    Kheifets, A. S.; Fursa, D. V.; Bray, I.; Colgan, J.; Pindzola, M. S.

    2010-08-01

    We extend our previous application of the convergent close-coupling (CCC) and time-dependent close-coupling (TDCC) methods [Phys. Rev. A10.1103/PhysRevA.81.023418 81, 023418 (2010)] to describe energy and angular resolved double photoionization (DPI) of lithium at arbitrary energy sharing. By doing so, we are able to evaluate the recoil ion momentum distribution of DPI of Li and make a comparison with recent measurements of Zhu [Phys. Rev. Lett.PRLTAO0031-900710.1103/PhysRevLett.103.103008 103, 103008 (2009)].

  11. Interference-encoded photoionization time delays in the hydrogen atom

    NASA Astrophysics Data System (ADS)

    Stodolna, A. S.; Lépine, F.; Rouzée, A.; Cohen, S.; Gijsbertsen, A.; Jungmann-Smith, J. H.; Bordas, C.; Vrakking, M. J. J.

    2017-08-01

    We present the observation of a checkerboard-like interference pattern in transverse momentum distributions measured for near-threshold photoionization of hydrogen atoms in a DC electric field. We analyze the pattern in terms of constructive and destructive interference between electron trajectories that directly leave the vicinity of the ion and indirect trajectories that remain in the vicinity of the ion for one or more orbital periods, and show that the interference pattern can be discussed in terms of ionization time delays between these two classes of trajectories.

  12. Correspondence of electron spectra from photoionization and nuclear internal conversion

    SciTech Connect

    Wark, D.L.; Bartlett, R.; Bowles, T.J.; Robertson, R.G.H.; Sivia, D.S.; Trela, W.; Wilkerson, J.F. ); Brown, G.S. ); Crasemann, B.; Sorensen, S.L.; Schaphorst, S.J. ); Knapp, D.A.; Henderson, J. ); Tulkki, J.; Aberg, T. )

    1991-10-21

    Electron energy spectra have been measured that result from {ital K}-shell ionization of Kr by two different mechanisms: (1) photoionization and (2) internal conversion in the decay of the isomeric state of {sup 83}Kr. It is demonstrated experimentally that these spectra, including satellites on the low-energy side of the primary 1{ital s}-electron peak, are identical. A theoretical interpretation of the identity of the spectra is given. The spectra agree well with a relativistic many-electron calculation in which the satellites are attributed to excitation and ionization of {ital M} and {ital N} electrons during the {ital K}-ionization process.

  13. Photoionization and absorption spectrum of formaldehyde in the vacuum ultraviolet.

    NASA Technical Reports Server (NTRS)

    Mentall, J. E.; Gentieu, E. P.; Krauss, M.; Neumann, D.

    1971-01-01

    The measurements have been conducted in the spectral range from 600 to 2000 A. Integrated oscillator strengths were determined for a number of strong Rydberg transitions above 1200 A. From the photoionization curve the first adiabatic ionization potential was found to be 10.87 plus or minus 0.01 eV. As an aid in interpreting the absorption spectrum, theoretical calculations were made using a single-configuration self-consistent field procedure for the Rydberg states and a model which included mixing between the Rydberg and valence states.

  14. Photoionization research on atomic radiation. 3: The ionization cross section of atomic nitrogen

    NASA Astrophysics Data System (ADS)

    Comes, F. J.; Elzer, A.

    1982-08-01

    The photoionization cross section of atomic nitrogen was measured between the ionization limit and 432 A. The experimental values are well fitted by those from a calculation of HENRY due to the dipole velocity approximation. A Rydberg series converging to the 5S-state of the ion is clearly identified from the ionization measurements and is shown to ionize.

  15. Absolute partial photoionization cross sections of ozone.

    SciTech Connect

    Berkowitz, J.; Chemistry

    2008-04-01

    Despite the current concerns about ozone, absolute partial photoionization cross sections for this molecule in the vacuum ultraviolet (valence) region have been unavailable. By eclectic re-evaluation of old/new data and plausible assumptions, such cross sections have been assembled to fill this void.

  16. Revealing isomerism in sodium-water clusters: Photoionization spectra of Na(H2O)n (n = 2-90)

    NASA Astrophysics Data System (ADS)

    Dierking, Christoph W.; Zurheide, Florian; Zeuch, Thomas; Med, Jakub; Parez, Stanislav; Slavíček, Petr

    2017-06-01

    Soft ionization of sodium tagged polar clusters is increasingly used as a powerful technique for sizing and characterization of small aerosols with possible application, e.g., in atmospheric chemistry or combustion science. Understanding the structure and photoionization of the sodium doped clusters is critical for such applications. In this work, we report on measurements of photoionization spectra for sodium doped water clusters containing 2-90 water molecules. While most of the previous studies focused on the ionization threshold of the Na(H2O)n clusters, we provide for the first time full photoionization spectra, including the high-energy region, which are used as reference for a comparison with theory. As reported in previous work, we have seen an initial drop of the appearance ionization energy with cluster size to values of about 3.2 eV for n <5 . In the size range from n = 5 to n = 15, broad ion yield curves emerge; for larger clusters, a constant range between signal appearance (˜2.8 eV) and signal saturation (˜4.1 eV) has been observed. The measurements are interpreted with ab initio calculations and ab initio molecular dynamics simulations for selected cluster sizes (n ≤ 15). The simulations revealed theory shortfalls when aiming at quantitative agreement but allowed us identifying structural motifs consistent with the observed ionization energy distributions. We found a decrease in the ionization energy with increasing coordination of the Na atom and increasing delocalization of the Na 3s electron cloud. The appearance ionization energy is determined by isomers with fully solvated sodium and a highly delocalized electron cloud, while both fully and incompletely solvated isomers with localized electron clouds can contribute to the high energy part of the photoionization spectrum. Simulations at elevated temperatures show an increased abundance of isomers with low ionization energies, an entropic effect enabling size selective infrared action

  17. Attosecond delays in photoionization: time and quantum mechanics

    NASA Astrophysics Data System (ADS)

    Maquet, Alfred; Caillat, Jérémie; Taïeb, Richard

    2014-10-01

    This article addresses topics regarding time measurements performed on quantum systems. The motivation is linked to the advent of ‘attophysics’ which makes feasible to follow the motion of electrons in atoms and molecules, with time resolution at the attosecond (1 as = 10-18 s) level, i.e. at the natural scale for electronic processes in these systems. In this context, attosecond ‘time-delays’ have been recently measured in experiments on photoionization and the question arises if such advances could cast a new light on the still active discussion on the status of the time variable in quantum mechanics. One issue still debatable is how to decide whether one can define a quantum time operator with eigenvalues associated to measurable ‘time-delays’, or time is a parameter, as it is implicit in the Newtonian classical mechanics. One objective of this paper is to investigate if the recent attophysics-based measurements could shed light on this parameter-operator conundrum. To this end, we present here the main features of the theory background, followed by an analysis of the experimental schemes that have been used to evidence attosecond ‘time-delays’ in photoionization. Our conclusion is that these results reinforce the view that time is a parameter which cannot be defined without reference to classical mechanics.

  18. Photoionization of atoms. Final report, April 1, 1976-March 30, 1981

    SciTech Connect

    Samson, J.A.R.; Starace, A.F.

    1981-11-01

    There were two main goals in the experimental study of photoionization. One was to provide accurate data on the results of photon-atom collisions, studying the absolute probability for ejecting electrons from specific orbitals and determining their angular distributions. Also of interest was the probability for one photon to eject two or more electrons. Another goal was to make measurements of specific interactions that would provide sensitive tests for the various theoretical approximations used in calculating photoionization cross sections. To achieve these two goals, care was taken in the selection of the various experiments and in the use of the most appropriate and sophisticated equipment. For example, the techniques of Photoelectron Spectroscopy, Photoionization - Mass Spectrometry, and Synchrotron radiation were used in many of the experiments.

  19. Experimental study of linear magnetic dichroism in photoionization satellite transitions of atomic rubidium

    SciTech Connect

    Jaenkaelae, K.; Alagia, M.; Feyer, V.; Richter, R.; Prince, K. C.

    2011-11-15

    Laser orientation in the initial state has been used to study the properties of satellite transitions in inner-shell photoionization of rubidium atoms. The linear magnetic dichroism in the angular distribution (LMDAD) has been utilized to probe the continuum waves of orbital angular momentum conserving monopole, and angular momentum changing conjugate satellites, accompanying the 4p ionization of atomic Rb. We show experimentally that LMDAD of both types of satellite transitions is nonzero and that LMDAD of monopole satellites, measured as a function of photon energy, mimics the LMDAD of direct photoionization, whereas the LMDAD of conjugate transitions deviates drastically from that trend. The results indicate that conjugate transitions cannot be described theoretically without explicit inclusion of electron-electron interaction. The present data can thus be used as a very precise test of current models for photoionization.

  20. Measuring the mechanical properties of molecular conformers

    PubMed Central

    Jarvis, S. P.; Taylor, S.; Baran, J. D.; Champness, N. R.; Larsson, J. A.; Moriarty, P.

    2015-01-01

    Scanning probe-actuated single molecule manipulation has proven to be an exceptionally powerful tool for the systematic atomic-scale interrogation of molecular adsorbates. To date, however, the extent to which molecular conformation affects the force required to push or pull a single molecule has not been explored. Here we probe the mechanochemical response of two tetra(4-bromophenyl)porphyrin conformers using non-contact atomic force microscopy where we find a large difference between the lateral forces required for manipulation. Remarkably, despite sharing very similar adsorption characteristics, variations in the potential energy surface are capable of prohibiting probe-induced positioning of one conformer, while simultaneously permitting manipulation of the alternative conformational form. Our results are interpreted in the context of dispersion-corrected density functional theory calculations which reveal significant differences in the diffusion barriers for each conformer. These results demonstrate that conformational variation significantly modifies the mechanical response of even simple porpyhrins, potentially affecting many other flexible molecules. PMID:26388232

  1. Study of X-ray photoionized Fe plasma and comparisons with astrophysical modeling codes

    SciTech Connect

    Foord, M E; Heeter, R F; Chung, H; vanHoof, P M; Bailey, J E; Cuneo, M E; Liedahl, D A; Fournier, K B; Jonauskas, V; Kisielius, R; Ramsbottom, C; Springer, P T; Keenan, K P; Rose, S J; Goldstein, W H

    2005-04-29

    The charge state distributions of Fe, Na and F are determined in a photoionized laboratory plasma using high resolution x-ray spectroscopy. Independent measurements of the density and radiation flux indicate the ionization parameter {zeta} in the plasma reaches values {zeta} = 20-25 erg cm s{sup -1} under near steady-state conditions. A curve-of-growth analysis, which includes the effects of velocity gradients in a one-dimensional expanding plasma, fits the observed line opacities. Absorption lines are tabulated in the wavelength region 8-17 {angstrom}. Initial comparisons with a number of astrophysical x-ray photoionization models show reasonable agreement.

  2. Energy dependence of photoion rotational distributions of N2 and CO

    NASA Astrophysics Data System (ADS)

    Choi, Heung Cheun; Rao, R. M.; Mihill, A. G.; Kakar, Sandeep; Poliakoff, E. D.; Wang, Kwanghsi; McKoy, V.

    1994-01-01

    We present the first measurements of rotational distributions for photoionization over extended energy ranges [0<=Ek<=200 eV for N2 (2σ-1u) and of 3<=Ek<=125 eV for CO (4σ-1)]. The N2 and CO results show a strikingly unusual and different energy dependence. Although differences are expected due to the absence of a center of symmetry in CO, detailed calculations reveal that this behavior arises from the presence of Cooper minima in the photoelectron continuum (kσg) in the case of N2 and from an f-wave shape resonance for 4σ-1 photoionization in CO.

  3. Vacancy cascades in small molecules following x-ray inner shell photoionization

    NASA Astrophysics Data System (ADS)

    Ray, D.; Dunford, R. W.; Southworth, S. H.; Kanter, E. P.; Doumy, G.; Gao, Y.; Ho, P. J.; Picon, A.

    2014-05-01

    We are investigating molecular effects in vacancy cascades of small molecules containing heavy atoms - IBr, Br2 and CH2BrI - following K-shell ionization. In addition to fundamental interest in the physics of such decay processes, there are practical applications such as medical treatments that use energetic fragmentation of iodinated compounds with high energy x-rays to selectively treat tumorous cells. Other biological applications are also promising. We utilize the tunable monochromatic x-ray beam at the Advanced Photon Source to trigger K-shell photoionization of Br and I, and measure charge distributions and the kinetic energies released to the fragment ions. A newly designed detection device allows us to do multi-fold coincidence measurements involving momentum imaging of all the ion fragments with very high detection efficiency in coincidence with x-ray fluorescence detection. By comparing the molecular fragmentation probabilities and the kinetic energies released in Br2, IBr and CH2BrI we aim to gain understanding of the fragmentation mechanism as a function of the bond distance between I and Br. Supported by the Chemical Sciences, Geosciences, and Biosciences Division, Office of Basic Energy Sciences, Office of Science, US Dept of Energy, Contract DE-AC02-06CH11357.

  4. HERSCHEL MEASUREMENTS OF MOLECULAR OXYGEN IN ORION

    SciTech Connect

    Goldsmith, Paul F.; Chen, Jo-Hsin; Li Di; Liseau, Rene; Black, John H.; Bell, Tom A.; Hollenbach, David; Kaufman, Michael J.; Lis, Dariusz C.; Melnick, Gary; Neufeld, David; Pagani, Laurent; Encrenaz, Pierre; Snell, Ronald; Benz, Arnold O.; Bruderer, Simon; Bergin, Edwin; Caselli, Paola; Caux, Emmanuel; Falgarone, Edith

    2011-08-20

    We report observations of three rotational transitions of molecular oxygen (O{sub 2}) in emission from the H{sub 2} Peak 1 position of vibrationally excited molecular hydrogen in Orion. We observed the 487 GHz, 774 GHz, and 1121 GHz lines using the Heterodyne Instrument for the Far Infrared on the Herschel Space Observatory, having velocities of 11 km s{sup -1} to 12 km s{sup -1} and widths of 3 km s{sup -1}. The beam-averaged column density is N(O{sub 2}) = 6.5 x 10{sup 16} cm{sup -2}, and assuming that the source has an equal beam-filling factor for all transitions (beam widths 44, 28, and 19''), the relative line intensities imply a kinetic temperature between 65 K and 120 K. The fractional abundance of O{sub 2} relative to H{sub 2} is (0.3-7.3) x 10{sup -6}. The unusual velocity suggests an association with a {approx}5'' diameter source, denoted Peak A, the Western Clump, or MF4. The mass of this source is {approx}10 M{sub sun} and the dust temperature is {>=}150 K. Our preferred explanation of the enhanced O{sub 2} abundance is that dust grains in this region are sufficiently warm (T {>=} 100 K) to desorb water ice and thus keep a significant fraction of elemental oxygen in the gas phase, with a significant fraction as O{sub 2}. For this small source, the line ratios require a temperature {>=}180 K. The inferred O{sub 2} column density {approx_equal}5 x 10{sup 18} cm{sup -2} can be produced in Peak A, having N(H{sub 2}) {approx_equal} 4 x 10{sup 24} cm{sup -2}. An alternative mechanism is a low-velocity (10-15 km s{sup -1}) C-shock, which can produce N(O{sub 2}) up to 10{sup 17} cm{sup -2}.

  5. Valence shell photoionization of SF6 and high harmonic generation

    NASA Astrophysics Data System (ADS)

    Jobin, Jobin; Fulfer, K.; Wilson, B.; Poliakoff, E.; Trallero, C.; Mondal, S.; Le, A.-T.; Lin, C.-D.; Lucchese, Robert

    2013-05-01

    When an atom or molecule is exposed to highly intense laser fields, the target can emit coherent radiation at photon energies which are multiples of incident laser energy. This process is known as High-order harmonic generation (HHG). There has been experimental and theoretical investigation of HHG for atoms and simple linear molecules. However, there have been few such studies for non-linear polyatomic molecules. In the current work, we investigate HHG for SF6 experimentally and theoretically. We employ quantitative rescattering theory (QRS) which makes use of the magnitude and phase of the dipole transition matrix elements for photoionization. For calculating dipole transition matrix elements we employ the ePolyscat static-exchange method. The features seen in the computed results will be compared to corresponding features in the measured HHG spectrum. The calculation is repeated for different polarization of incident laser and different intensities. The analysis allows us to reproduce then understand experimentally measured HHG spectra from SF6. Additionally, the valence shell photoionization parameters are also compared with several other theoretical and experimental results.

  6. Localization of a continuum shape resonance - Photoionization of CS2

    NASA Astrophysics Data System (ADS)

    Kakar, Sandeep; Choi, Heung-Cheun; Poliakoff, E. D.

    1992-10-01

    We report a vibrationally resolved investigation into the 5sigma(u) exp -1 shape-resonant ionization dynamics for CS2 in the range h nu 18-30 eV. The intensity of dispersed fluorescence from CS2(+)(B 2Sigma(u)(+) photoions is measured to obtain partial photoionization cross-section curves for the v = (0,0,0) and (1,0,0) levels of CS2(+)(B 2Sigma(u)(+), as well as the vibrational branching ratio. Our results indicate a shape resonance at hv equal to about 21 eV which is insensitive to changes in the symmetric stretching coordinate. These data are consistent with recent theoretical efforts that predict a shape resonance in the 5sigma(u) - epsilon pi(g) channel. All previous vibrationally resolved data on shape resonances have been obtained for systems whose shape resonances occur in the (epsilon sigma) continuum. The current results are in contrast to behavior observed for other shape resonances, highlighting both their diverse nature and possible extensions of the current measurements.

  7. Photoionization mass spectrometry of combustion radicals. Final technical report

    SciTech Connect

    Cool, T.A.

    1998-12-31

    Fundamental research on the combustion of halogenated organic compounds with emphasis on reaction pathways leading to the formation of chlorinated organic compounds and the development of continuous emission monitoring methods will assist in DOE efforts in the management and control of hazardous chemical wastes. Selective laser ionization techniques are used in the laboratory for the measurement of concentration profiles of radical intermediates in chlorinated hydrocarbon flames. A novel flame-sampling VUV laser photoionization mass spectrometer, constructed with DOE funding, is in use for these studies. Progress is reported here on the use of this new facility in the development, refinement, and verification of chemical kinetic models describing the thermal destruction of toxic chlorocarbons commonly found in chemical wastes. In the past two years the author has used the flame sampling VUV laser ionization mass spectrometer system for studies of chlorocarbon-doped methane/oxygen flames. Relative concentration profiles and photoionization efficiency curves have been measured for over two-dozen key reaction intermediates. Preliminary kinetic models have been developed that promise an improved understanding of chlorocarbon chemistry under laboratory flame conditions.

  8. Vibrationally resolved C 1s photoionization cross section of CF4

    NASA Astrophysics Data System (ADS)

    Patanen, M.; Kooser, K.; Argenti, L.; Ayuso, D.; Kimura, M.; Mondal, S.; Plésiat, E.; Palacios, A.; Sakai, K.; Travnikova, O.; Decleva, P.; Kukk, E.; Miron, C.; Ueda, K.; Martín, F.

    2014-06-01

    The differential photoionization cross section ratio (ν = 1)/(ν = 0) for the symmetric stretching mode in the C 1s photoionization of CF4 was studied both theoretically and experimentally. We observed this ratio to differ from the Franck-Condon ratio and to be strongly dependent on the photon energy, even far from the photoionization threshold. The density-functional theory computations show that the ratio is significantly modulated by the diffraction of the photoelectrons by the neighbouring atoms at high photon energies. At lower energies, the interpretation of the first very strong maximum observed about 60 eV above the photoionization threshold required detailed calculations of the absolute partial cross sections, which revealed that the absolute cross section has two maxima at lower energies, which turn into one maximum in the cross section ratio because the maxima appear at slightly different energies in ν = 1 and ν = 0 cross sections. These two strong, low-energy continuum resonances originate from the trapping of the continuum wavefunction in the molecular potential of the surrounding fluorine atoms and from the outgoing electron scattering by them.

  9. Photoionization of endohedral fullerenes using soft x-ray coincidence spectroscopy

    NASA Astrophysics Data System (ADS)

    Obaid, Razib; Xiong, Hui; Ablikim, Utuq; Augustin, Sven; Schnorr, Kirsten; Battistoni, Andrea; Wolf, Thomas; Carroll, Ann Marie; Bilodeau, Rene; Osipov, Timur; Rolles, Daniel; Berrah, Nora

    2016-05-01

    Endohedral fullerenes are a model system to understand the reorganization dynamics of highly charged molecular systems with delocalized electronic clouds in the multiphoton excitation regime. Previous experiments at the Linac Coherent Light Source (LCLS) using free-electron laser (FEL) and ultrafast IR laser pulses studied this feature in Ho3N@C80. The question remains whether these dynamics can be studied in the site-specific single photo-ionization regime. Ho3N@C80 is particularly interesting since the inner molecule, Ho3N, is unstable in its natural form. The presence of the encapsulating cage, with the charge exchange characteristics of Holmium, stabilizes the whole molecule. In this study, we will present the charge fragmentation dynamics of this species in the single photoionization process of inner shell electrons (4d) of Holmium using the Advanced Light Source (ALS) at LBNL. Photoion-photoion correlation data, alongside with qualitative electron data will be presented. Funded by the DoE-BES, Grant No. DE-SC0012376.

  10. Absolute single-photoionization cross sections of Se2 +: Experiment and theory

    NASA Astrophysics Data System (ADS)

    Macaluso, D. A.; Aguilar, A.; Kilcoyne, A. L. D.; Red, E. C.; Bilodeau, R. C.; Phaneuf, R. A.; Sterling, N. C.; McLaughlin, B. M.

    2015-12-01

    Absolute single-photoionization cross-section measurements for Se2 + ions were performed at the Advanced Light Source at Lawrence Berkeley National Laboratory using the merged-beams photo-ion technique. Measurements were made at a photon energy resolution of 24 ±3 meV in the photon energy range 23.5-42.5 eV, spanning the ground state and low-lying metastable state ionization thresholds. To clearly resolve the resonant structure near the ground-state threshold, high-resolution measurements were made from 30.0 to 31.9 eV at a photon energy resolution of 6.7 ±0.7 meV. Numerous resonance features observed in the experimental spectra are assigned and their energies and quantum defects tabulated. The high-resolution cross-section measurements are compared with large-scale, state-of-the-art theoretical cross-section calculations obtained from the Dirac Coulomb R -matrix method. Suitable agreement is obtained over the entire photon energy range investigated. These results are an experimental determination of the absolute photoionization cross section of doubly ionized selenium and include a detailed analysis of the photoionization resonance spectrum of this ion.

  11. Photoionization of Au+ ions and developments in the synthesis of the metallofullerene Au@C60

    NASA Astrophysics Data System (ADS)

    Bogolub, Kyren; Macaluso, David; Mueller, Allison; Johnson, Andrea; Müller, Alfred; Schippers, Stefan; Hellhund, Jonas; Borovik, Alexander; Anders, Andre; Aguilar, Alex; Kilcoyne, A. L. David

    2014-05-01

    Single photoionization of Au+ ions was investigated via the merged-beams technique at AMO Beamline 10.0.1.2 of the Advanced Light Source at Lawrence Berkeley National Laboratory. The relative single photoionization yield was measured as a function of photon energy in the 45 eV to 120 eV energy range. These measurements were made in preparation for future photoionization studies of the endohedral metallofullerene Au@C60, the production of which was also investigated. In proof-of-principle measurements a mass-resolved beam of Au@C60+was produced with a primary ion beam current in the single picoamp range without optimization of the ion source or synthesis parameters. Plans are presented for improved metallofullere production yield to be used in photoionization measurements of the endohedral fullerene ions in conjunction with the continuing study of pure Au. We would like to acknowledge the generous sharing of equipment vital to this work by Andre Anders, the Plasma Applications group leader at the Advanced Light Source, LBNL.

  12. An imaging photoelectron-photoion coincidence investigation of homochiral 2R,3R-butanediol clusters

    NASA Astrophysics Data System (ADS)

    Daly, Steven; Powis, Ivan; Garcia, Gustavo A.; Tia, Maurice; Nahon, Laurent

    2017-07-01

    We report an experimental investigation of homochiral cluster formation in seeded molecular beam expansions of (2R,3R)-butanediol. Synchrotron radiation vacuum ultraviolet photoionization measurements have been performed using a double imaging electron-ion spectrometer in various configurations and modes of operation. These include measurements of the cluster ion mass spectra, wavelength scanned ion yields, and threshold electron spectra. Protonated cluster ions ranging up to n = 7 have been observed and size-selected photoelectron spectra and photoelectron circular dichroism (PECD) have been recorded by velocity map imaging, recorded in coincidence with ions, at a number of fixed photon energies. Translation temperatures of the cluster ions have been further examined by ion imaging measurements. As well as the sequence of protonated clusters with integral numbers of butanediol monomer units, a second series with half-integral monomer masses is observed and deduced to result from a facile cleavage of a butanediol monomer moiety within the nascent cluster. This second sequence of half-integral masses displays quite distinct behaviours. PECD measurements are used to show that the half-integral mass cluster ions do not share a common parentage with whole integer masses. Using an analogy developed with simple theoretical calculations of butanediol dimer structures, it is inferred that the dissociative branching into integral and half-integral ion mass sequences is controlled by the presence of different butanediol monomer conformations within the hydrogen bonded clusters.

  13. Molecular conductance measurements through printed Au nanodots

    NASA Astrophysics Data System (ADS)

    Jiang, W.; Garfunkel, E.; Zhitenev, N.; Abusch-Magder, D.; Tennant, D.; Bao, Z.

    2006-09-01

    Gold pads with ˜100nm diameter are imprinted on self-assembled monolayers of alkane dithiols of different lengths using nanotransfer printing. The pads are contacted by conductive atomic force microscope tips, and electron transport was measured as a function of force. Atomic scale topography at the metal-molecule interface is essential to describe the conductance-stress relationship. A finite force (1-10nN) deforms devices resulting in two competing effects: (a) a larger contact area and (b) deformation of the interfacial bonds and/or tilting of the molecules. The estimated conductance of molecules is significantly smaller than results suggested in previous experiments and calculations.

  14. Sturmian approach to the study of photoionization of atoms and molecules

    NASA Astrophysics Data System (ADS)

    Granados Castro, Carlos Mario; Ancarani, Lorenzo Ugo; Gasaneo, Gustavo; Mitnik, Dario M.

    2013-09-01

    In this presentation we study the photoionization of atoms and molecules using ultrashort laser pulses, solving the time-independent Schrödinger equation (TISE) in a first order perturbation theory. The interaction laser-matter is described with the dipolar operator in the velocity gauge. Generalized Sturmian functions are used to solve the driven equation for a scattering wave function which includes all the information about the ionization problem. For the atomic case, we study the photoionization of He atom using the Hermann-Skillman potential together with the one-active electron approximation. For molecular systems (CH4 in this work), we use first a spherically symmetric potential Ui(r), and then a more realistic potential that includes all the nuclei and other electrons interaction, as in. For each molecular orbital we use Moccia's wave functions, solve the TISE with an initial molecular orbital i of the ground state and extract the corresponding photoionization cross sections. For both atomic and molecular systems we compare our results with previous calculations and available experimental data.

  15. Time-dependent Cooling in Photoionized Plasma

    NASA Astrophysics Data System (ADS)

    Gnat, Orly

    2017-02-01

    I explore the thermal evolution and ionization states in gas cooling from an initially hot state in the presence of external photoionizing radiation. I compute the equilibrium and nonequilibrium cooling efficiencies, heating rates, and ion fractions for low-density gas cooling while exposed to the ionizing metagalactic background radiation at various redshifts (z = 0 ‑ 3), for a range of temperatures (108–104 K), densities (10‑7–103 cm‑3), and metallicities (10‑3–2 times solar). The results indicate the existence of a threshold ionization parameter, above which the cooling efficiencies are very close to those in photoionization equilibrium (so that departures from equilibrium may be neglected), and below which the cooling efficiencies resemble those in collisional time-dependent gas cooling with no external radiation (and are thus independent of density).

  16. Photoionization of atomic hydrogen in electric field

    SciTech Connect

    Gorlov, Timofey V; Danilov, Viatcheslav V

    2010-01-01

    Laser assisted ionization of high energy hydrogen beams in magnetic fields opens wide application possibilities in accelerator physics and other fields. The key theoretical problem of the method is the calculation of the ionization probability of a hydrogen atom affected by laser and static electric fields in the particle rest frame. A method of solving this problem with the temporal Schr dinger equation including a continuum spectrum is presented in this paper in accurate form for the first time. This method allows finding the temporal evolution of the wave function of the hydrogen atom as a function of laser and static electric fields. Solving the problem of photoionization reveals quantum effects that cannot be described by the cross sectional approach. The effects play a key role in the problems of photoionization of H0 beams with the large angular or energy spread.

  17. Emission spectra of photoionized plasmas induced by intense EUV pulses: Experimental and theoretical investigations

    NASA Astrophysics Data System (ADS)

    Saber, Ismail; Bartnik, Andrzej; Skrzeczanowski, Wojciech; Wachulak, Przemysław; Jarocki, Roman; Fiedorowicz, Henryk

    2017-03-01

    Experimental measurements and numerical modeling of emission spectra in photoionized plasma in the ultraviolet and visible light (UV/Vis) range for noble gases have been investigated. The photoionized plasmas were created using laser-produced plasma (LPP) extreme ultraviolet (EUV) source. The source was based on a gas puff target; irradiated with 10ns/10J/10Hz Nd:YAG laser. The EUV radiation pulses were collected and focused using grazing incidence multifoil EUV collector. The laser pulses were focused on a gas stream, injected into a vacuum chamber synchronously with the EUV pulses. Irradiation of gases resulted in a formation of low temperature photoionized plasmas emitting radiation in the UV/Vis spectral range. Atomic photoionized plasmas produced this way consisted of atomic and ionic with various ionization states. The most dominated observed spectral lines originated from radiative transitions in singly charged ions. To assist in a theoretical interpretation of the measured spectra, an atomic code based on Cowan's programs and a collisional-radiative PrismSPECT code have been used to calculate the theoretical spectra. A comparison of the calculated spectral lines with experimentally obtained results is presented. Electron temperature in plasma is estimated using the Boltzmann plot method, by an assumption that a local thermodynamic equilibrium (LTE) condition in the plasma is validated in the first few ionization states. A brief discussion for the measured and computed spectra is given.

  18. Toward Rotational State-Selective Photoionization of ThF+ Ions

    NASA Astrophysics Data System (ADS)

    Zhou, Yan; Ng, Kia Boon; Gresh, Dan; Cairncross, William; Grau, Matt; Ni, Yiqi; Cornell, Eric; Ye, Jun

    2016-06-01

    ThF+ has been chosen to replace HfF+ for a second-generation measurement of the electric dipole moment of the electron (eEDM). Compared to the currently running HfF+ eEDM experiment, ThF+ has several advantages: (i) the eEDM-sensitive state (3Δ1) is the ground state, which facilitates a long coherence time [1]; (ii) its effective electric field (35 GV/cm) is 50% larger than that of HfF+, which promises a direct increase of the eEDM sensitivity [2]; and (iii) the ionization energy of neutral ThF is lower than its dissociation energy, which introduces greater flexibility in rotational state-selective photoionization via core-nonpenetrating Rydberg states [3]. In this talk, we first present our strategy of preparing and utilizing core-nonpenetrating Rydberg states for rotational state-selective ionization. Then, we report spectroscopic data of laser-induced fluorescence of neutral ThF, which provides critical information for multi-photon ionization spectroscopy. [1] D. N. Gresh, K. C. Cossel, Y. Zhou, J. Ye, E. A. Cornell, Journal of Molecular Spectroscopy, 319 (2016), 1-9 [2] M. Denis, M. S. Nørby, H. J. A. Jensen, A. S. P. Gomes, M. K. Nayak, S. Knecht, T. Fleig, New Journal of Physics, 17 (2015) 043005. [3] Z. J. Jakubek, R. W. Field, Journal of Molecular Spectroscopy 205 (2001) 197-220.

  19. Neon photoionized plasma experiment at Z

    NASA Astrophysics Data System (ADS)

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

    2016-10-01

    We discuss an experimental effort to study the atomic kinetics in neon photoionized plasmas via K-shell line absorption spectroscopy. The experiment employs the intense x-ray flux emitted at the collapse of a Z-pinch to heat and backlight a photoionized plasma contained within a cm-scale gas cell placed at various distances from the Z-pinch and filled with neon gas pressures in the range from 3.5 to 30 torr. The experimental platform affords an order of magnitude range in the ionization parameter characterizing the photoionized plasma from about 3 to 80 erg*cm/s. An x-ray crystal spectrometer capable of collecting both time-integrated and time-gated spectra is used to collect absorption spectra. A suite of IDL programs has been developed to process the experimental data to produce transmission spectra. The spectra show line absorption by several ionization stages of neon, including Be-, Li-, He-, and H-like ions. Analysis of these spectra yields ion areal-densities and charge state distributions, which can be compared with results from atomic kinetics codes. In addition, the electron temperature is extracted from level population ratios of nearby energy levels in Li- and Be-like ions, which can be used to test heating models of photoionized plasmas. This work was sponsored in part by the DOE National Nuclear Security Administration Grant DE-FG52-09NA29551, DOE Office of Science Grant DE-SC0014451, and the Z Facility Fundamental Science Program of SNL.

  20. Space shuttle molecular and wake vacuum measurements

    NASA Technical Reports Server (NTRS)

    Naumann, R. J.; Carignan, G. R.; Miller, E. R.

    1985-01-01

    The wake environment of the space shuttle is analyzed to determine whether it is feasible to perform ultrahigh vacuum experiments in or near the payload bay with the shuttle oriented such that the payload bay faces the antivelocity direction. Several mechanisms were considered by which molecules could approach the payload bay from this direction and their relative contributions to the wake environment are estimated. These mechanisms include ambient atmospheric molecules that have velocities in excess of the orbital velocity which can overtake the shuttle, ambient atmospheric molecules that are backscattered by collisions with the shuttle induced atmosphere, and self scattering from the induced atmosphere. These estimates are compared with the measurements made with the collimated mass spectrometer which was part of the Induced Environment Contamination Monitor flown on several of the early shuttle flights. Although the collimated mass spectrometer was not designed for this purpose and the instrument background for the species for which the collimator is effective is above the expected levels, upper limits can be established for these species in the wake environment which are consistent with the analysis. There was considerably more helium and argon observed in the wake direction than was predicted, however. Possible origins of these gases are discussed.

  1. Kr photoionized plasma induced by intense extreme ultraviolet pulses

    SciTech Connect

    Bartnik, A. Wachulak, P.; Fiedorowicz, H.; Skrzeczanowski, W.

    2016-04-15

    Irradiation of any gas with an intense EUV (extreme ultraviolet) radiation beam can result in creation of photoionized plasmas. The parameters of such plasmas can be significantly different when compared with those of the laser produced plasmas (LPP) or discharge plasmas. In this work, the photoionized plasmas were created in a krypton gas irradiated using an LPP EUV source operating at a 10 Hz repetition rate. The Kr gas was injected into the vacuum chamber synchronously with the EUV radiation pulses. The EUV beam was focused onto a Kr gas stream using an axisymmetrical ellipsoidal collector. The resulting low temperature Kr plasmas emitted electromagnetic radiation in the wide spectral range. The emission spectra were measured either in the EUV or an optical range. The EUV spectrum was dominated by emission lines originating from Kr III and Kr IV ions, and the UV/VIS spectra were composed from Kr II and Kr I lines. The spectral lines recorded in EUV, UV, and VIS ranges were used for the construction of Boltzmann plots to be used for the estimation of the electron temperature. It was shown that for the lowest Kr III and Kr IV levels, the local thermodynamic equilibrium (LTE) conditions were not fulfilled. The electron temperature was thus estimated based on Kr II and Kr I species where the partial LTE conditions could be expected.

  2. Photoionization sensor CES for non-invasive medical diagnostics

    NASA Astrophysics Data System (ADS)

    Mustafaev, Aleksandr; Rastvorova, Iuliia; Khobnya, Kristina; Podenko, Sofia

    2016-10-01

    Method CES (collisional electron spectroscopy), patented in Russia, the USA, Japan, China, Germany and Britain, allows to analyze the gaseous mixtures using electron spectroscopy under high pressures up to atmospheric without using vacuum. The design of VUV photoionization detector was developed based on this method. Such detector is used as a portable gas analyzer for continuous personal bio-medical monitoring. This detector measures energy of electrons produced in ionization with resonance photons, whose wavelength situated in the vacuum ultraviolet (VUV). Nowadays, micro plasma source of such photons on resonant line of Kr with energy of 10,6 eV is developed. Only impurities are ionized and detected by the VUV-emission, meanwhile the main components of air stay neutral that reduces background signal and increases the sensibility along with accuracy. The experimental facilities with VUV photoionization sensors CES are constructed with the overall sizes about 10*10*1 mm. The watt consumption may comprise less than 1W. Increase of electrometer amplifier's sensibility and more high-aperture construction are used today to increase the sensibility of CES-detectors. The wide range of detectable molecules and high sensitivity allow the development of portable device, which can become the base of the future preventive medicine. Work supported by Foundation for Assistance to Small Innovative Enterprises in Science and Technology.

  3. Laser isotope separation of lithium by two-step photoionization

    SciTech Connect

    Saleem, M.; Hussain, Shahid; Rafiq, M.; Baig, M. A.

    2006-09-01

    Lithium isotope separation has been achieved employing the two-step photoionization technique along with a narrow band dye laser in conjunction with a time of flight mass spectrometer. The demonstrated method yields a high degree of selectivity by tuning the dye laser at the resonance levels of Li{sup 6} and Li{sup 7}. It is inferred that the concentration of the natural abundance of the Li{sup 6} isotope gets enhanced up to over 47% as the exciter dye laser is tuned to the {sup 2}P{sub 1/2} of Li{sup 6} even if the linewidth of the exciter laser is not sufficiently narrow to excite the isotopic level. It is also noticed that the much higher energy density of the exciter laser limits the resolution of the fine structure levels of the lithium isotopes that leads to a loss in the enrichment of Li{sup 6} due to the power-broadening effect. Measurements of the photoionization cross section of the lithium isotopes from the 2p {sup 2}P{sub 1/2,3/2}, excited states for Li{sup 6} and Li{sup 7} and the corresponding number densities are reported.

  4. Molecular Architecture Studied by the Surface Forces Measurement.

    PubMed

    Kurihara, Kazue

    2016-11-29

    This feature article reviews the surface forces measurement as a tool for studying molecular architecture chemistry. The history of the measurement is briefly described in the Introduction. The general overview covers specific features of the surface forces measurement as a tool for studying and using molecular architecture. This measurement is powerful for understanding interaction forces and for characterizing and discovering the phenomena at solid-liquid interfaces and soft complex matter. An apparatus for opaque samples was developed, which can be used to study not only opaque samples in various media but also electrochemical processes under various electrochemical potentials. Our studies of molecular architecture are reviewed; they include biological molecular recognition especially involved in the enzyme-substrate interaction; polyelectrolyte brushes exhibiting steric repulsion, which can be reproduced by the osmotic pressure of the counterions, and a density-dependent transition; the hydrogen-bonded molecular macrocluster formation of alcohol and carboxylic acids adsorbed on silica in nonpolar solvents such as cyclohexane; and surface forces between ferrocene-modified electrodes under various applied potentials. These studies demonstrate how the forces measurement is used to identify interacting species such as in biological systems to reveal unknown phenomena and to characterize soft complex matter and the effective potential of the electrodes. Readers will be introduced to the broad applications of the force measurement.

  5. Molecular transport in collagenous tissues measured by gel electrophoresis.

    PubMed

    Hunckler, Michael D; Tilley, Jennifer M R; Roeder, Ryan K

    2015-11-26

    Molecular transport in tissues is important for drug delivery, nutrient supply, waste removal, cell signaling, and detecting tissue degeneration. Therefore, the objective of this study was to investigate gel electrophoresis as a simple method to measure molecular transport in collagenous tissues. The electrophoretic mobility of charged molecules in tissue samples was measured from relative differences in the velocity of a cationic dye passing through an agarose gel in the absence and presence of a tissue section embedded within the gel. Differences in electrophoretic mobility were measured for the transport of a molecule through different tissues and tissue anisotropy, or the transport of different sized molecules through the same tissue. Tissue samples included tendon and fibrocartilage from the proximal (tensile) and distal (compressive) regions of the bovine flexor tendon, respectively, and bovine articular cartilage. The measured electrophoretic mobility was greatest in the compressive region of the tendon (fibrocartilage), followed by the tensile region of tendon, and lowest in articular cartilage, reflecting differences in the composition and organization of the tissues. The anisotropy of tendon was measured by greater electrophoretic mobility parallel compared with perpendicular to the predominate collagen fiber orientation. Electrophoretic mobility also decreased with increased molecular size, as expected. Therefore, the results of this study suggest that gel electrophoresis may be a useful method to measure differences in molecular transport within various tissues, including the effects of tissue type, tissue anisotropy, and molecular size.

  6. Photoionization Cross Section of Xe{sup +} Ion in the Pure 5p{sup 5} {sup 2}P{sub 3/2} Ground Level

    SciTech Connect

    Thissen, R.; Bizau, J. M.; Blancard, C.; Coreno, M.; Franceschi, P.; Giuliani, A.; Nicolas, C.

    2008-06-06

    Coupling an ion trap with synchrotron radiation is shown here to be a powerful approach to measure photoionization cross sections on ionic species relaxed in their ground state. The photoionization efficiency curve of Xe{sup +} ions stored in a Fourier transform ion cyclotron resonance ion trap was recorded at ELETTRA in the 20-23 eV photon energy range. Absolute cross sections were derived by comparison of the photoionization yield of Xe{sup +} with measurements from the ASTRID merged-beam experiment. Multiconfiguration Dirac-Fock calculations were performed for the interpretation of these new data.

  7. Photoionization of atoms and molecules. [of hydrogen, helium, and xenon

    NASA Technical Reports Server (NTRS)

    Samson, J. A. R.

    1976-01-01

    A literature review on the present state of knowledge in photoionization is presented. Various experimental techniques that have been developed to study photoionization, such as fluorescence and photoelectron spectroscopy, mass spectroscopy, are examined. Various atoms and molecules were chosen to illustrate these techniques, specifically helium and xenon atoms and hydrogen molecules. Specialized photoionization such as in positive and negative ions, excited states, and free radicals is also treated. Absorption cross sections and ionization potentials are also discussed.

  8. DISSOCIATIVE PHOTOIONIZATION OF POLYCYCLIC AROMATIC HYDROCARBON MOLECULES CARRYING AN ETHYNYL GROUP

    SciTech Connect

    Rouillé, G.; Krasnokutski, S. A.; Fulvio, D.; Jäger, C.; Henning, Th.; Garcia, G. A.; Tang, X.-F.; Nahon, L.

    2015-09-10

    The life cycle of the population of interstellar polycyclic aromatic hydrocarbon (PAH) molecules depends partly on the photostability of the individual species. We have studied the dissociative photoionization of two ethynyl-substituted PAH species, namely, 9-ethynylphenanthrene and 1-ethynylpyrene. Their adiabatic ionization energy and the appearance energy of fragment ions have been measured with the photoelectron photoion coincidence spectroscopy technique. The adiabatic ionization energy has been found at 7.84 ± 0.02 eV for 9-ethynylphenanthrene and at 7.41 ± 0.02 eV for 1-ethynylpyrene. These values are similar to those determined for the corresponding non-substituted PAH molecules phenanthrene and pyrene. The appearance energy of the fragment ion indicative of the loss of a H atom following photoionization is also similar for either ethynyl-substituted PAH molecule and its non-substituted counterpart. The measurements are used to estimate the critical energy for the loss of a H atom by the PAH cations and the stability of ethynyl-substituted PAH molecules upon photoionization. We conclude that these PAH derivatives are as photostable as the non-substituted species in H i regions. If present in the interstellar medium, they may play an important role in the growth of interstellar PAH molecules.

  9. Double K-shell photoionization and hypersatellite x-ray transitions of 12{<=}Z{<=}23 atoms

    SciTech Connect

    Hoszowska, J.; Dousse, J.-Cl.; Cao, W.; Fennane, K.; Kayser, Y.; Szlachetko, M.; Szlachetko, J.; Kavcic, M.

    2010-12-15

    Single-photon double K-shell ionization of low-Z neutral atoms in the range 12{<=}Z{<=}23 is investigated. The experimental method was based on measurements of the high-resolution K{alpha}{sup h} hypersatellite x-ray spectra following the radiative decay of the K-shell double-vacancy states excited by monochromatic synchrotron radiation. The photon energy dependence of the double K-shell ionization was measured over a wide range of photon energies from threshold up to and beyond the maximum of the double-to-single photoionization cross section ratios. From the high-resolution x-ray emission spectra the energies and linewidths of the hypersatellite transitions, as well as the K{alpha}{sub 1}{sup h}:K{alpha}{sub 2}{sup h} intensity ratios, were determined. The relative importance of the initial-state and final-state electron-electron interactions to the K-shell double photoionization is addressed. Physical mechanisms and scaling laws of the K-shell double photoionization are examined. A semiempirical universal scaling of the double-photoionization cross sections with the effective nuclear charge for neutral atoms in the range 2{<=}Z{<=}47 is established.

  10. Dissociative Photoionization of Polycyclic Aromatic Hydrocarbon Molecules Carrying an Ethynyl Group

    NASA Astrophysics Data System (ADS)

    Rouillé, G.; Krasnokutski, S. A.; Fulvio, D.; Jäger, C.; Henning, Th.; Garcia, G. A.; Tang, X.-F.; Nahon, L.

    2015-09-01

    The life cycle of the population of interstellar polycyclic aromatic hydrocarbon (PAH) molecules depends partly on the photostability of the individual species. We have studied the dissociative photoionization of two ethynyl-substituted PAH species, namely, 9-ethynylphenanthrene and 1-ethynylpyrene. Their adiabatic ionization energy and the appearance energy of fragment ions have been measured with the photoelectron photoion coincidence spectroscopy technique. The adiabatic ionization energy has been found at 7.84 ± 0.02 eV for 9-ethynylphenanthrene and at 7.41 ± 0.02 eV for 1-ethynylpyrene. These values are similar to those determined for the corresponding non-substituted PAH molecules phenanthrene and pyrene. The appearance energy of the fragment ion indicative of the loss of a H atom following photoionization is also similar for either ethynyl-substituted PAH molecule and its non-substituted counterpart. The measurements are used to estimate the critical energy for the loss of a H atom by the PAH cations and the stability of ethynyl-substituted PAH molecules upon photoionization. We conclude that these PAH derivatives are as photostable as the non-substituted species in H i regions. If present in the interstellar medium, they may play an important role in the growth of interstellar PAH molecules.

  11. Similarity Measure for Molecular Structure: A Brief Review

    NASA Astrophysics Data System (ADS)

    Bero, S. A.; Muda, A. K.; Choo, Y. H.; Muda, N. A.; Pratama, S. F.

    2017-09-01

    Similarity or distance measures have been used widely to calculate the similarity or dissimilarity between two samples of dataset. Cheminformatics is known as the domain that dealing with chemical information and both similarity and distance coefficient have been an important role for matching, searching and classification of chemical information. There are various types of similarity/distance coefficient used in molecular structure similarity searching. Generally, the calculation using similarity/distance coefficient is focusing more on 2-dimensional (2D) rather than 3-dimensional (3D) structure. In this paper, the popular similarity/distance coefficients for molecular structure will be reviewed together with the review on 3D molecular structure.

  12. Photodissociation of Small Molecules and Photoionization of Free Radicals Using the VUV Velocity-Map Imaging Photoion and Photoelectron Method

    NASA Astrophysics Data System (ADS)

    Gao, Hong

    The tunable vacuum ultraviolet (VUV) laser generated through the two-photon resonance-enhanced four-wave mixing scheme is combined with the newly developed time-slice velocity map imaging photoion method to study the photodissociation of small molecules in the VUV region, and with the velocity map imaging photoelectron method to study the photoionization of free radicals. The photodissociation dynamics of NO in the energy region around 13.5 eV has been investigated. Branching ratios of the three lowest dissociation channels of 12C 16O that produce C(3P) + O(3P), C( 1D) + O(3P) and C(3P) + O(1D) are measured for the first time in the VUV region from 102,500 cm-1 to 110,500 cm-1, valuable information of the dissociation dynamics for this prototype system has been deduced. We demonstrated an experiment that has two independently tunable VUV lasers and a time-slice velocity map imaging setup, this provides us a global way to perform systematic state-selected photodissociation of small molecules via state-selected detection of the atomic products in the VUV region. The velocity map imaging photoelectron method was successfully used to obtain the photoelectron spectrum of the propargyl radical (C3H3) via a single VUV photoionization process. The propargyl radical is generated by the 193 nm laser photodissociation of the precursor C3H3Cl. This is the first time that the velocity map imaging photoelectron method is used to get the photoelectron spectra of free radicals, indicating that it is a powerful technique for studying the photoionization of free radicals which are always hard to be produced with high enough number densities for spectroscopic studies. This dissertation is mainly based on the following peer-reviewed journal articles: 1. Hong Gao, Yang Pan, Lei Yang, Jingang Zhou, C. Y. Ng and William M. Jackson. "Time-slice velocity-map ion imaging studies of the Photodissociation of NO in the vacuum ultraviolet region", the Journal of Chemical Physics, 136, 134302

  13. Dissociative photoionization of 1,2-dichloroethane in intense near-infrared femtosecond laser field

    NASA Astrophysics Data System (ADS)

    Zhang, Jian; Yang, Yan; Li, Zhipeng; Zhang, Shian; Sun, Zhenrong

    2017-01-01

    We experimentally demonstrate the dissociative photoionization of 1,2-C2H4Cl2 molecules in femtosecond laser field by time-of-flight mass spectrum and dc-slice imaging technology. Our results show the low kinetic energy components are from the dissociative ionization process of singly charged molecular ions, and the positive charge assignment are greatly influenced by the appearance energy of the fragment ions. The high kinetic energy components result from Coulomb explosion of multi-charged molecular ions, and the different angular distribution of these fragments along Csbnd C and Csbnd Cl bond dissociation can be explained by the potential energy surfaces of the molecular ions.

  14. A molecular fraction method for measuring personnel radiation doses

    NASA Astrophysics Data System (ADS)

    Fadel, M. A.; Khalil, W. A.; Krodja, R. P.; Sheta, N.; Abd El-Baset, M. S.

    1987-02-01

    This work represents a development in fast and albedo neutron and gamma ray dosimetry, using cellulose nitrate, as a tissue equivalent material, in which radiation damage was registered. The changes in molecular fractions of the polymer were measured after irradiation with neutron fluences from a 252Cf source in the range 10 5-10 10 n/cm 2 and gamma doses in the range 10 -4-10 -1 Gy through the use of gel filtration chromatography. Effects of irradiation on phantom, phantom to dosimeter distance, phantom thickness and storage at extreme environmental conditions were studied on the detector response and readout. The results showed that main chain scission followed by formation of new molecular configurations is the predominant effect of radiation on the polymer. The method enables measurements of neutron fluences and gamma doses in mixed radiation fields. Empirical formulae for calculating the absorbed dose from the measured changes in molecular fraction intensities are given.

  15. Photoion rotational distributions from near-threshold to deep in the continuum

    NASA Astrophysics Data System (ADS)

    Poliakoff, E. D.; Choi, Heung Cheun; Rao, R. M.; Mihill, A. G.; Kakar, Sandeep; Wang, Kwanghsi; McKoy, V.

    1995-08-01

    We present the first measurements of ion rotational distributions for photoionization over an extended range [0≤EK≤200 eV for N2 (2σ-1u) and 3≤EK≤125 eV for CO (4σ-1)]. The N2 ion rotational distributions are seen to change dramatically over this energy range, indicating that characteristically molecular behavior of the photoelectron persists far from ionization threshold. In addition, the N2 and CO results show a strikingly different dependence on energy. Although differences are expected due to the absence of a center of symmetry in CO, detailed calculations reveal that this behavior arises from the presence of Cooper minima in the 2σu→kσg continuum in the case of N2 and from an f-wave shape resonance in the 4σ→kσ channel in CO. Agreement between measured and calculated ion rotational distributions is excellent. The N2 results are also compared with electron bombardment ionization data. This comparison demonstrates that previous interpretations of electron bombardment data are prone to errors.

  16. Heats of vaporization of room temperature ionic liquids by tunable vacuum ultraviolet photoionization

    SciTech Connect

    Chambreau, Steven D.; Vaghjiani, Ghanshyam L.; To, Albert; Koh, Christine; Strasser, Daniel; Kostko, Oleg; Leone, Stephen R.

    2009-11-25

    The heats of vaporization of the room temperature ionic liquids (RTILs) N-butyl-N-methylpyrrolidinium bistrifluorosulfonylimide, N-butyl-N-methylpyrrolidinium dicyanamide, and 1-butyl-3-methylimidazolium dicyanamide are determined using a heated effusive vapor source in conjunction with single photon ionization by a tunable vacuum ultraviolet synchrotron source. The relative gas phase ionic liquid vapor densities in the effusive beam are monitored by clearly distinguished dissociative photoionization processes via a time-of-flight mass spectrometer at a tunable vacuum ultraviolet beamline 9.0.2.3 (Chemical Dynamics Beamline) at the Advanced Light Source synchrotron facility. Resulting in relatively few assumptions, through the analysis of both parent cations and fragment cations, the heat of vaporization of N-butyl-N-methylpyrrolidinium bistrifluorosulfonylimide is determined to be Delta Hvap(298.15 K) = 195+-19 kJ mol-1. The observed heats of vaporization of 1-butyl-3-methylimidazolium dicyanamide (Delta Hvap(298.15 K) = 174+-12 kJ mol-1) and N-butyl-N-methylpyrrolidinium dicyanamide (Delta Hvap(298.15 K) = 171+-12 kJ mol-1) are consistent with reported experimental values using electron impact ionization. The tunable vacuum ultraviolet source has enabled accurate measurement of photoion appearance energies. These appearance energies are in good agreement with MP2 calculations for dissociative photoionization of the ion pair. These experimental heats of vaporization, photoion appearance energies, and ab initio calculations corroborate vaporization of these RTILs as intact cation-anion ion pairs.

  17. Desorption and ionization mechanisms in desorption atmospheric pressure photoionization.

    PubMed

    Luosujärvi, Laura; Arvola, Ville; Haapala, Markus; Pól, Jaroslav; Saarela, Ville; Franssila, Sami; Kotiaho, Tapio; Kostiainen, Risto; Kauppila, Tiina J

    2008-10-01

    The factors influencing desorption and ionization in newly developed desorption atmospheric pressure photoionization-mass spectrometry (DAPPI-MS) were studied. Redirecting the DAPPI spray was observed to further improve the versatility of the technique: for dilute samples, parallel spray with increased analyte signal was found to be the best suited, while for more concentrated samples, the orthogonal spray with less risk for contamination is recommended. The suitability of various spray solvents and sampling surface materials was tested for a variety of analytes with different polarities and molecular weights. As in atmospheric pressure photoionization, the analytes formed [M + H](+), [M - H](-), M(+*), M(-*), [M - H + O](-), or [M - 2H + 2O](-) ions depending on the analyte, spray solvent, and ionization mode. In positive ion mode, anisole and toluene as spray solvents promoted the formation of M(+*) ions and were therefore best suited for the analysis of nonpolar compounds (anthracene, benzo[a]pyrene, and tetracyclone). Acetone and hexane were optimal spray solvents for polar compounds (MDMA, testosterone, and verapamil) since they produced intensive [M + H](+) ion peaks of the analytes. In negative ion mode, the type of spray solvent affected the signal intensity, but not the ion composition. M(-*) ions were formed from 1,4-dinitrobenzene, and [M - H + O](-) and [M - 2H + 2O](-) ions from 1,4-naphthoquinone, whereas acidic compounds (naphthoic acid and paracetamol) formed [M - H](-) ions. The tested sampling surfaces included various materials with different thermal conductivities. The materials with low thermal conductivity, i.e., polymers like poly(methyl methacrylate) and poly(tetrafluoroethylene) (Teflon) were found to be the best, since they enable localized heating of the sampling surface, which was found to be essential for efficient analyte desorption. Nevertheless, the sampling surface material did not affect the ionization mechanisms.

  18. Photoionization of isoelectronic ions: Mg{sup +} and Al{sup 2+}

    SciTech Connect

    Aguilar, A.; West, J.B.; Phaneuf, R.A.; Brooks, R. L.; Folkmann, F.; Kjeldsen, H.; Bozek, J.D.; Schlachter, A.S.; Cisneros, C.

    2003-01-01

    High-resolution measurements of the photoionization cross sections of the Na-isoelectronic ions Mg{sup +} and Al{sup 2+} are presented, to be compared with earlier measurements in which structure in the most prominent peaks was unresolved. These measurements have been normalized to the earlier ones in order to provide values of the oscillator strengths of the newly resolved peaks, and comparison is made with multiconfiguration Hartree-Fock calculations.

  19. Long Duration Directional Drives for Star Formation and Photoionization

    SciTech Connect

    Kane, J. O.; Martinez, D. A.; Pound, M. W.; Heeter, R. F.; Villette, B.; Casner, A.; Mancini, R. C.

    2015-06-18

    This research will; confirm the possibility of studying the structure and evolution of star-forming regions of molecular clouds in the laboratory; test the cometary model for the formation of the pillar structures in molecular clouds; assess the effect of magnetic fields on the evolution of structures in molecular clouds; and develop and demonstrate a new, long-duration (60-100 ns), directional source of x-ray radiation that can be used for the study of deeply nonlinear hydrodynamics, hydrodynamic instabilities that occur in the presence of directional radiation, shock-driven and radiatively-driven collapse of dense cores, and photoionization. Due to the iconic status of the pillars of the Eagle Nebula, this research will bring popular attention to plasma physics, HED laboratory physics, and fundamental science at NIF and other experimental facilities. The result will be to both to bring new perspectives to the studies of hydrodynamics in inertial confinement fusion and HED scenarios in general, and to promote interest in the STEM disciplines.

  20. Recent development of the photoionization / PDR code Cloudy

    NASA Astrophysics Data System (ADS)

    van Hoof, P. A. M.; Porter, R. L.; Ferland, G. J.

    2011-05-01

    Cloudy is a widely used open-source modeling tool for photoionized and PDR/XDR environments. It was the first code that could produce a unified and fully self-consistent model of both the ionized region and the PDR surrounding a central source. Such an environment can e.g. be found in massive star forming regions, in planetary nebulae or around AGN. The code is also capable of producing "classical" PDR models that do not include an ionized region. The emphasis of the code is on detailed and state-of-the-art treatment of micro-physical processes. Cloudy is continually being updated to improve this treatment and to add more and newer atomic and molecular data. On this poster we will discuss some of these developments, including the addition of the LAMDA, CDMS and JPL molecular line databases. These will allow us to make NLTE predictions for the molecular line emission, but the accuracy of those predictions will be limited by the quality (or even absence) of collision strength data. We will discuss the impact this has on the accuracy of the predicted spectra in typical ISM conditions.

  1. Molecular Dications and the Auroral Mystery Feature: Measurements on Nitrogen

    NASA Astrophysics Data System (ADS)

    Daw, A. N.; Brewer, S. M.; Estes, C. C.; Kanoy, J. A.; Myer, B. W.; Calamai, A. G.

    2006-05-01

    Experiments in progress at the ASU ion trapping facility will provide atomic and molecular data for N^+, N2^++, and N2, specifically, measurements of: the radiative lifetime of the ^5S metastable level of N^+, the dissociation rate of N2^++, electron capture rates from molecular nitrogen for both these ions, and the cross section for dissociative electron impact ionization of molecular nitrogen into metastable ^5S N^+. Ions are created in a radiofrequency ion trap by electron bombardment on nitrogen gas, and both the number of stored ions and the UV radiation emitted by the stored ion population (from decaying metastable N^+(^5S) ions and N2^+++N2 reactions) are measured as a function of time. Preliminary data and results will be presented

  2. Complete characterization of double photoionization processes

    NASA Astrophysics Data System (ADS)

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

    2011-06-01

    We analyze correlated photoelectron spectra of single-photon two-electron ionization [double photoionization (DPI)] of helium to reconstruct the phase of the spectral amplitude of this process. The phase can be reconstructed reliably in a wide range of photoelectron momenta, thus allowing one to retrieve information about the wave function of the DPI process and its temporal evolution. Our simulation indicates that the proposed phase reconstruction technique can be applied in experiment to trace dynamics of the DPI process with attosecond precision.

  3. Complete characterization of double photoionization processes

    SciTech Connect

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

    2011-06-15

    We analyze correlated photoelectron spectra of single-photon two-electron ionization [double photoionization (DPI)] of helium to reconstruct the phase of the spectral amplitude of this process. The phase can be reconstructed reliably in a wide range of photoelectron momenta, thus allowing one to retrieve information about the wave function of the DPI process and its temporal evolution. Our simulation indicates that the proposed phase reconstruction technique can be applied in experiment to trace dynamics of the DPI process with attosecond precision.

  4. K-shell photoionization cross-sections.

    NASA Technical Reports Server (NTRS)

    Daltabuit, E.; Cox, D. P.

    1972-01-01

    Approximate values for the threshold energies, threshold cross sections, and energy dependence of the cross sections for K-shell photoionization are tabulated for H, He, C, N, O, Ne, Mg, Si, and S in all stages of ionization. The approximation of these data is based on the assumptions that the threshold energy is a simple function of the nuclear charge and the number of electrons present in the atom, and that the threshold values and energy dependence of the cross sections are determined only by the threshold energy.

  5. Photoionization of zinc by TDLDA calculations

    NASA Astrophysics Data System (ADS)

    Stener, M.; Decleva, P.

    1997-10-01

    Absolute photoionization cross section profiles of Zn have been calculated at TDLDA and LDA level, employing a very accurate B-spline basis set and the modified Sternheimer approach. The van Leeuwen - Baerends exchange correlation potential has been used, since its correct asymptotic behaviour is able to support virtual states and describe core-excited resonances. A comparison with available theoretical and experimental data has been performed when possible. The present method has been proven to be robust to analyse wide photon energy regions (from threshold up to 200 eV) and discuss the various shapes of one-electron resonances.

  6. Identification and Chemistry of Phenylnitrene in Premixed Pyridine/Oxygen/Argon Flame with Tunable Synchrotron Photoionization

    NASA Astrophysics Data System (ADS)

    Tian, Zhen-yu; Yuan, Tao; Wang, Jing; Li, Yu-yang; Zhang, Tai-chang; Zhu, Ai-guo; Qi, Fei

    2007-08-01

    The triplet state phenylnitrene (PhN) species generated from the low-pressure (4.0 kPa) premixed laminar pyridine/oxygen/argon flame was detected and identified using tunable synchrotron vacuum ultraviolet photoionization and molecular-beam mass spectrometry techniques. The ionization energies of PhN were determined experimentally by photoionization efficiency spectra and theoretically by calculations. The results indicate that PhN has a 3A2 ground state and its first and second adiabatic ionization energies are 8.04 and 9.15±0.05 eV, respectively. Furthermore, the formation and consumption pathways of PhN are proposed according to the species detected in the present work. PhN is the first nitrogen-containing diradical detected in combustion chemistry, and so it should be added to the kinetic model of pyridine flames.

  7. Double-photoionization of CO few eV above threshold

    NASA Astrophysics Data System (ADS)

    Belkacem, A.; Osipov, T.; Hertlein, M.; Prior, M.; Adaniya, H.; Feinberg, B.; Weber, Th.; Jahnke, T.; Dorner, R.; Schmidt, L.; Schoffler, M.; Jagutzki, O.; Cocke, C. L.; Landers, A.

    2006-05-01

    We measured double photoionization of CO molecules at 48 eV photon energy. The double ionization of CO produces mostly C^+ + O^+ fragments with non-measurable amounts of CO^2+. The formation of C^+ + O^+ can proceed through two possible channels: a) Direct ionization of two electron into the continuum -- similar to the H2 double ionization -- direct channel. b) Ionization of one electron into the continuum followed by autoionization of a second electron -- Indirect channel. The electron distribution measured with a COLTRIMS shows a very clear distinction of the direct and indirect channels. The kinetic energy release spectrum shows a series of peaks corresponding to the transient vibrational states of the various electronic states of (CO^2+)*. These states are similar to previous measurements at higher energies (K-shell photoionization). (CO^2+)* is found to predissociate through a ^3σ^- and ^1δ dissociative states leading to considerably faster dissociation times than natural lifetimes of the electronic bound states.

  8. Direct double photoionization of the valence shell of Be

    SciTech Connect

    Citrini, F.; Malegat, L.; Selles, P.; Kazansky, A.K.

    2003-04-01

    The hyperspherical R-matrix method with semiclassical outgoing waves is used to study the direct double photoionization (DPI) of the valence shell of the lightest alkaline earth-metal Be. The absolute fully integrated, singly, doubly, and triply differential cross sections obtained are compared with the single set of measurements available and with recent calculations based on the convergent close coupling and time-dependent close coupling methods. The level of agreement between all these data is very encouraging. A comparison is also made between the DPI of He and the direct DPI of the valence shell of Be. It confirms that the electron-electron correlations are stronger in the valence 2s shell of Be than in the 1s shell of He, thus contributing to a desirable clarification.

  9. Photoionizing Trapped Highly Charged Ions with Synchrotron Radiation

    SciTech Connect

    Crespo, J R; Simon, M; Beilmann, C; Rudolph, J; Steinbruegge, R; Eberle, S; Schwarz, M; Baumann, T; Schmitt, B; Brunner, F; Ginzel, R; Klawitter, R; Kubicek, K; Epp, S; Mokler, P; Maeckel, V; Ullrich, J; Brown, G V; Graf, A; Leutenegger, M; Beiersdorfer, P; Behar, E; Follath, R; Reichardt, G; Schwarzkopf, O

    2011-09-12

    Photoabsorption by highly charged ions plays an essential role in astrophysical plasmas. Diagnostics of photoionized plasmas surrounding binary systems rely heavily on precise identification of absorption lines and on the knowledge of their cross sections and widths. Novel experiments using an electron beam ion trap, FLASH EBIT, in combination with monochromatic synchrotron radiation allow us to investigate ions in charge states hitherto out of reach. Trapped ions can be prepared in any charge state at target densities sufficient to measure absorption cross sections below 0.1 Mb. The results benchmark state-of-the-art predictions of the transitions wavelengths, widths, and absolute cross sections. Recent high resolution results on Fe{sup 14+}, Fe{sup 15+}, and Ar{sup 12+} at photon energies up to 1 keV are presented.

  10. Laser resonance photoionization spectroscopy of Rydberg levels in Fr

    SciTech Connect

    Andreev, S.V.; Letokhov, V.S.; Mishin, V.I.

    1987-09-21

    We investigated for the first time the high-lying Rydberg levels in the rare radioactive element francium (Fr). The investigations were conducted by the highly sensitive laser resonance atomic photoionization technique with Fr atoms produced at a rate of about 10/sup 3/ atoms/s in a hot cavity. We measured the wave numbers of the 7p/sup 2/P/sub 3/2/..-->..nd/sup 2/D (n = 22--33) and 7p/sup 2/P/sub 3/2/..-->..ns/sup 2/S (n = 23, 25--27,29--31) transitions and found the binding energy of the 7p/sup 2/P/sub 3/2/ state to be T = -18 924.8(3) cm/sup -1/, which made it possible to establish accurately the ionization potential of Fr.

  11. Precision assessment of biofluid viscosity measurements using molecular rotors.

    PubMed

    Akers, Walter J; Haidekker, Mark A

    2005-06-01

    Blood viscosity changes with many pathologic conditions, but its importance has not been fully investigated because the current methods of measurement are poorly suited for clinical applications. The use of viscosity-sensitive fluorescent molecular rotors to determine fluid viscosity in a nonmechanical manner has been investigated recently, but it is unknown how the precision of the fluorescence-based method compares to established mechanical viscometry. Human blood plasma viscosity was modulated with high-viscosity plasma expanders, dextran, pentastarch, and hetastarch. The samples were divided into a calibration and a test set. The relationship between fluorescence emission and viscosity was established using the calibration set. Viscosity of the test set was determined by fluorescence and by cone-and-plate viscometer, and the precision of both methods compared. Molecular rotor fluorescence intensity showed a power law relationship with solution viscosity. Mechanical measurements deviated from the theoretical viscosity value by less than 7.6%, while fluorescence-based measurements deviated by less than 6%. The average coefficient of variation was 6.9% (mechanical measurement) and 3.4% to 3.8% (fluorescence-based measurement, depending on the molecular rotor used). Fluorescence-based viscometry exhibits comparable precision to mechanical viscometry. Fluorescence viscometry does not apply shear and is therefore more practical for biofluids which have apparent non-Newtonian properties. In addition, fluorescence instrumentation makes very fast serial measurements possible, thus promising new areas of application in laboratory and clinical settings.

  12. Studies of x-ray emission properties of photoionized plasmas

    NASA Astrophysics Data System (ADS)

    Wang, Feilu; Han, Bo; Jin, Rui; Salzmann, David; Liang, Guiyun; Wei, Huigang; Zhong, Jiayong; Zhao, Gang; Li, Jia-ming

    2016-03-01

    In this paper three aspects of photoionized plasmas are discussed in both laboratory and astrophysical contexts. First, the importance of accurate atomic/ionic data for the analysis of photoionized plasmas is shown. Second, an overview of present computer codes for the analysis of photoionized plasmas is given. We introduce our computer model, radiative-collisional code based on the flexible atomic code (RCF), for calculations of the properties of such plasmas. RCF uses database generated by the flexible atomic code. Using RCF it is shown that incorporating the satellite lines from doubly excited Li-like ions into the He{}α triplet lines is necessary for reliable analysis of observational spectra from astrophysical objects. Finally, we introduce a proposal to generate photoionized plasmas by x-ray free electron laser, which may facilitate the simulation in lab of astrophysical plasmas in photoionization equilibrium.

  13. Double photoionization of helium with synchrotron x-rays: Proceedings

    SciTech Connect

    Not Available

    1994-01-01

    This report contains papers on the following topics: Overview and comparison of photoionization with charged particle impact; The ratio of double to single ionization of helium: the relationship of photon and bare charged particle impact ionization; Double photoionization of helium at high energies; Compton scattering of photons from electrons bound in light elements; Electron ionization and the Compton effect in double ionization of helium; Elimination of two atomic electrons by a single energy photon; Double photoionization of helium at intermediate energies; Double Photoionization: Gauge Dependence, Coulomb Explosion; Single and Double Ionization by high energy photon impact; The effect of Compton Scattering on the double to single ionization ratio in helium; and Double ionization of He by photoionization and Compton scattering. These papers have been cataloged separately for the database.

  14. Photodissociation and photoionization of organosulfur radicals

    SciTech Connect

    Hsu, Chia-Wei

    1994-05-27

    The dynamics of S(3P2,1,0, 1D2) production from the 193 nm photodissociation of CH3SCH3, H2S and CH3SH have been studied using 2 + 1 resonance-enhanced multiphoton ionization (REMPI) techniques. The 193 nm photodissociation cross sections for the formation of S from CH3S and HS initially prepared in the photodissociation of CH3SCH3 and H2S are estimated to be 1 x 10-18 and 1.1 x 10-18 cm2, respectively. The dominant product from CH3S is S(1D), while that from SH is S(3P). Possible potential energy surfaces involved in the 193 nm photodissociation of CH3S($\\tilde{X}$) and SH(X) have been also examined. Threshold photoelectron (PE) spectra for SH and CH3S formed in the ultraviolet photodissociation of H2S and CH3SH, respectively, have been measured using the nonresonant two-photon pulsed field ionization (N2P-PFI) technique. The rotationally resolved N2P-PFI-PE spectrum obtained for SH indicates that photoionization dynamics favors the rotational angular momentum change ΔN < 0 with the ΔN value up to -3, an observation similar to that found in the PFI-PE spectra of OH (OD) and NO. The ionization energies for SH(X2Π3,2) and CH3S($\\tilde{X}$2E3/2) are determined to be 84,057.5 ± 3 cm-1 and 74,726 ± 8 cm-1 respectively. The spin-orbit splittings for SH(X2Π3/2, 1/2) and CH3S($\\tilde{X}$2E3/2, 1/2) are found to be 377 ± 2 and 257 ± 5 cm-1, respectively, in agreement with previous measurements. The C-S stretching frequency for CH3S+($\\tilde{X}$3A2) is 733 ± 5 cm-1. This study illustrates that the PFI-PE detection method can be a

  15. Shining a light on galactic outflows: photoionized outflows

    NASA Astrophysics Data System (ADS)

    Chisholm, John; Tremonti, Christy A.; Leitherer, Claus; Chen, Yanmei; Wofford, Aida

    2016-04-01

    We study the ionization structure of galactic outflows in 37 nearby, star-forming galaxies with the Cosmic Origins Spectrograph on the Hubble Space Telescope. We use the O I, Si II, Si III, and Si IV ultraviolet absorption lines to characterize the different ionization states of outflowing gas. We measure the equivalent widths, line widths, and outflow velocities of the four transitions, and find shallow scaling relations between them and galactic stellar mass and star formation rate. Regardless of the ionization potential, lines of similar strength have similar velocities and line widths, indicating that the four transitions can be modelled as a comoving phase. The Si equivalent width ratios (e.g. Si IV/Si II) have low dispersion, and little variation with stellar mass; while ratios with O I and Si vary by a factor of 2 for a given stellar mass. Photoionization models reproduce these equivalent width ratios, while shock models under predict the relative amount of high ionization gas. The photoionization models constrain the ionization parameter (U) between -2.25 < log (U) < -1.5, and require that the outflow metallicities are greater than 0.5 Z⊙. We derive ionization fractions for the transitions, and show that the range of ionization parameters and stellar metallicities leads to a factor of 1.15-10 variation in the ionization fractions. Historically, mass outflow rates are calculated by converting a column density measurement from a single metal ion into a total hydrogen column density using an ionization fraction, thus mass outflow rates are sensitive to the assumed ionization structure of the outflow.

  16. Vacuum ultraviolet photoionization mass spectra and cross-sections for volatile organic compounds at 10.5 eV.

    PubMed

    Kanno, Nozomu; Tonokura, Kenichi

    2007-08-01

    Vacuum ultraviolet single-photon ionization time-of-flight mass spectrometry (VUV-SPI-TOFMS) has been applied to the detection of volatile organic compounds (VOCs), including aromatic, chlorinated, and oxygenated compounds. Photoionization mass spectra of 23 VOCs were measured using SPI-TOFMS at 10.5 eV (118 nm). The limits of detection of VOCs using SPI-TOFMS at 10.5 eV were estimated to be a few ppbv. The mass spectra of 20 VOCs exhibit only the parent ion and its isotopes' signals. The ionization processes of the VOCs were discussed on the basis of the reaction enthalpies predicted by the quantum chemical calculations. Absolute photoionization cross-sections for 23 VOCs, including 12 newly measured VOCs, at 10.5 eV were determined in comparison to the reported absolute photoionization cross-section of NO.

  17. Molecular force sensors to measure stress in cells

    NASA Astrophysics Data System (ADS)

    Prabhune, Meenakshi; Rehfeldt, Florian; Schmidt, Christoph F.

    2017-06-01

    Molecularly generated forces are essential for most activities of biological cells, but also for the maintenance of steady state or homeostasis. To quantitatively understand cellular dynamics in migration, division, or mechanically guided differentiation, it will be important to exactly measure stress fields within the cell and the extracellular matrix. Traction force microscopy and related techniques have been established to determine the stress transmitted from adherent cells to their substrates. However, different approaches are needed to directly assess the stress generated inside the cell. This has recently led to the development of novel molecular force sensors. In this topical review, we briefly mention methods used to measure cell-external forces, and then summarize and explain different designs for the measurement of cell-internal forces with their respective advantages and disadvantages.

  18. Mode specific photoionization dynamics in polyatomic molecules

    NASA Astrophysics Data System (ADS)

    Rathbone, Gerald Jeffery

    2002-11-01

    The work presented in this dissertation presents new work on polyatomic photoionization. In these investigations, the broad range behavior of both allowed and forbidden vibrational modes in linear triatomic systems were studied to understand mode specific aspects of photoionization. The current study is made possible by the experimental strategy of exploiting high resolution photoelectron spectroscopy and the high brightness of third generation synchrotron radiation sources. The data is taken typically tens of eV's past the ionization potential. The strategy that I employ is to probe alternative vibrational modes which are frequently affected differently following resonant ionization. Such vibrationally resolved data can be used to understand how the correlation between vibration and electron energy reveals microscopic insights into the photoelectron scattering process. Moreover, the mode specific behavior contains a wealth of information not only regarding allowed transitions, but also contains information on how forbidden transitions gain surprising amounts of intensity. A previously overlooked mechanism for the appearance of forbidden nontotally symmetric vibrations was discovered---resonantly amplified vibronic symmetry breaking. The photoelectron the culprit for the symmetry breaking which induces the excitation of nominally forbidden vibrational excitations. In a more general sense, these results will demonstrate that some fundamental spectroscopic approximations are not always valid, and can lead to surprising consequences.

  19. On the ionization and dissociative photoionization of iodomethane: a definitive experimental enthalpy of formation of CH3I.

    PubMed

    Bodi, Andras; Shuman, Nicholas S; Baer, Tomas

    2009-12-14

    The dissociative photoionization onset energy of the CH(3)I --> CH(3)(+) + I reaction was studied at the vacuum ultraviolet (VUV) beamline of the Swiss Light Source (SLS) using a new imaging photoelectron photoion coincidence (iPEPICO) apparatus operating with a photon resolution of 2 meV and a threshold electron kinetic energy resolution of about 1 meV. Three previous attempts at establishing this value accurately, namely a pulsed field ionization (PFI)-PEPICO measurement, ab initio calculations and a mass-analyzed threshold ionization (MATI) experiment, in which the onset energy was bracketed by state-selected excitation to vibrationally excited (2)A(1) A states of the parent ion, have yielded contradictory results. It is shown that dimers and adducts formed in the supersonic molecular beam affected the PFI-PEPICO onset energy. The room temperature iPEPICO experiment yields an accurate 0 K onset of 12.248 +/- 0.003 eV, from which we derive a Delta(f)H(o)(298 K)(CH(3)I) = 15.23 +/- 0.3 kJ mol(-1), and the C-I bond energy in CH(3)I is 232.4 +/- 0.4 kJ mol(-1). The room temperature breakdown diagram shows a fine structure that corresponds to the threshold photoelectron spectrum (TPES) of the A state. Low internal energy neutrals seem to be preferentially ionized in the A state when compared with the X state, and A state peaks in the TPES are Stark-shifted as a function of the DC field, whereas the dissociative photoionization of X state ions is not affected. This suggests that there are different competing mechanisms at play to produce ions in the A state vs. ions in the X state. The competition between field ionization and autoionization in CH(3)I is compared with that in Ar, N(2) and in the H-atom loss energy region in CH(4)(+). The binding energies of the neutral and ionic Ar-CH(3)I clusters were found to be 26 and 66 meV, respectively.

  20. Shape resonances in the photoionization of CF4

    SciTech Connect

    Stephens, J. A.; Dill, Dan; Dehmer, Joseph L.

    1986-01-01

    Calculations of photoionization cross sections and photoelectron angular distributions have been performed for all occupied orbitals of CF4 using the multiple-scattering model. Results are compared with very recent experiments which employ synchrotron radiation to measure these quantities, namely the measurements of Truesdale e t a l. for the carbonK shell, and measurements of Carlson e t a l. and Novak e t a l. for the five outermost valence levels. The calculations predict intense shape resonances below 3 eV in continua of a1 and t2 final state symmetry. Qualitative agreement is attained on comparing much of the theory with experiment, notably the five outer valence levels, which serves to establish a one-electron picture of the photoionization dynamics of CF4.

  1. Femtosecond time-resolved EUV photoion imaging studies of pure helium nanodroplets

    NASA Astrophysics Data System (ADS)

    Buenermann, Oliver; Kornilov, Oleg; Gessner, Oliver; Leone, Stephen R.; Neumark, Daniel M.

    2010-03-01

    Helium nanodroplets provide a cryogenic, weakly interacting matrix for the isolation and spectroscopy of molecules and clusters. The relaxation dynamics of electronically excited helium nanodroplets are investigated by femtosecond time resolved photoion imaging studies. The droplets are excited into a broad absorption band centered at 23.8 eV. The electronic and nuclear dynamics following this excitation are monitored by photoionization with a 785nm probe pulse. A Wiley-McLaren time of flight spectrometer equipped with a time- and position sensitive delay line detector facilitates the measurement of mass selective ion kinetic energy distributions. First measurements reveal differences in the kinetic energy release of the Helium monomer, dimer and trimer ions. Furthermore, the pump-probe time-delay dependent ion spectra exhibit several features evolving on various timescales. The combination of these results with previously recorded photoelectron imaging measurements allows for a new level of insight into the electronic and nuclear dynamics of electronically excited helium nanodroplets.

  2. Measuring molecular flows with high-resolution stimulated Raman spectroscopy

    NASA Technical Reports Server (NTRS)

    She, C. Y.; Fairbank, W. M., Jr.; Exton, R. J.

    1981-01-01

    It is proposed to use high-resolution stimulated Raman spectroscopy to directly measure high-speed molecular flow velocities in wind tunnels and in combustive chambers. A feasibility study indicates that flow speeds from Mach 0.04 up may be measured with the proposed method using available laser systems. It is pointed out that the success of the proposed technique will make it possible to measure all interesting flow parameters, i.e., species concentration, temperature, and velocity, in a time of less than 1 microsecond at a repetition rate of 10,000/s using a single experimental arrangement.

  3. Multiple Point Dynamic Gas Density Measurements Using Molecular Rayleigh Scattering

    NASA Technical Reports Server (NTRS)

    Seasholtz, Richard; Panda, Jayanta

    1999-01-01

    A nonintrusive technique for measuring dynamic gas density properties is described. Molecular Rayleigh scattering is used to measure the time-history of gas density simultaneously at eight spatial locations at a 50 kHz sampling rate. The data are analyzed using the Welch method of modified periodograms to reduce measurement uncertainty. Cross-correlations, power spectral density functions, cross-spectral density functions, and coherence functions may be obtained from the data. The technique is demonstrated using low speed co-flowing jets with a heated inner jet.

  4. A case for chiral contributions to nondipole effects in photoionization using linearly polarized soft x-rays

    NASA Astrophysics Data System (ADS)

    Bowen, Kyle Patrick

    Modelling angular distributions of photoelectrons requires making accurate approximations of both the incoming light and the behavior of bound electrons. The experimental determination of photoelectron angular distributions is crucial to the development of accurate theoretical models governing the light-matter interaction. To date, many models have relied upon the dipole approximation, which assumes a constant electric field as the source of ionization. Despite knowing that the dipole approximation would break down as photon energy increased, the precise limit was unclear. Over the past two decades, a strong case has been made that corrections to the dipole approximation are necessary for accurately describing photoionization using soft x-rays (100 - 1000 eV). This energy region is widely studied, as it has become more readily accessible thanks to third-generation synchrotron radiation facilities. This work provides experimental evidence for first-order corrections to the dipole approximation, known as nondipole effects, for atoms and molecules, focusing on Xe 3d photoionization, which showcases the role of interchannel coupling in nondipole angular distributions, N 1s photoionization from molecular nitrogen in an attempt to settle a dispute over molecular nondipole effects, and C 1s photoionization from the chiral molecule camphor, which provides the first-ever experimental determination of a theoretically predicted chiral-specific nondipole effect. All of the experiments were performed using electron time-of-flight spectroscopy at the Advanced Light Source (ALS) at Lawrence Berkeley National Laboratory (LBNL).

  5. Inner-shell photoexcitations as probes of the molecular ions CH+, OH+, and SiH+: Measurements and theory

    NASA Astrophysics Data System (ADS)

    Mosnier, J.-P.; Kennedy, E. T.; van Kampen, P.; Cubaynes, D.; Guilbaud, S.; Sisourat, N.; Puglisi, A.; Carniato, S.; Bizau, J.-M.

    2016-06-01

    Spectral probes for the CH+, OH+, and SiH+ hydride molecular ions that play key roles in astrophysics and plasma processes are presented. The merged-beam technique at the SOLEIL synchrotron was used to record the photoionization (ion yield) spectra of CH+, OH+, and SiH+ and that of their parent atomic ions, in the K -shell and L -shell regions, respectively. Energies and oscillator strengths for the K α (CH+ and OH+) and L α (SiH+) transitions were determined from the spectra. Ab initio calculations interpret the experimental data in terms of contributions from ground and excited valence electronic states.

  6. High-resolution threshold photoelectron-photoion coincidence experiments performed on beamline 9.0.2.2: Kinetic energy release study of the process SF{sub 6} + hv {yields} SF{sub 5}{sup +} F + e{sup -}

    SciTech Connect

    Evans, M.; Ng, C.Y.; Hsu, C.W.; Heimann, P.

    1997-04-01

    Vacuum ultraviolet (VUV) photoionization mass spectrometry has been used extensively to determine the energetics of neutral radicals and radical cations, as well as to study the dynamics of the dissociative photoionization process. Very often these measurements are concerned with determining the appearance energy (AE) for a dissociative ionization process, as well as determining the heats of formation of the species involved. One such photoionization mass spectrometric technique employed on End Station 2 of the Chemical Dynamics Beamline (9.0.2.2) at the Advanced Light Source is the threshold photoelectron-photoion coincidence (TPEPICO) method. TPEPICO involves measuring the time-of-flight (TOF) mass spectrum of a given cation in coincidence with threshold photoelectrons at a known photoionization energy.

  7. A dissociative photoionization study of the c4Σu- state in O+2 using the TPEPICO technique

    NASA Astrophysics Data System (ADS)

    Padmanabhan, A.; MacDonald, M. A.; Ryan, C. H.; Zuin, L.; Reddish, T. J.

    2012-11-01

    In the dissociative photoionization (DPI) process, hν + O2 → O + O+ + e-, ionisation and dissociation both occur (either as a direct or indirect process) following photoabsorption. The Threshold Photoelectron Photoion Coincidence (TPEPICO) technique, i.e. measuring the coincidence yield between threshold photoelec-trons and photoions is a powerful way of studying the dynamics involved. The c4Σu- state in O+2 at ~ 24.56 eV has a shallow minimum in its potential that supports two distinct quasi-bound vibrational levels (v = 0, 1). We have investigated the angular distributions of 2 eV O+(4S) ions produced from DPI of O +2 c4Σu- (v = 0, 1) using the TPEPICO technique.

  8. Vacuum-Ultraviolet (VUV) Photoionization of Small Methanol and Methanol-Water Clusters

    SciTech Connect

    Kostko, Oleg; Belau, Leonid; Wilson, Kevin R.; Ahmed, Musahid

    2008-04-24

    In this work, we report on the vacuum-ultraviolet (VUV) photoionization of small methanol and methanol-water clusters. Clusters of methanol with water are generated via co-expansion of the gas phase constituents in a continuous supersonic jet expansion of methanol and water seeded in Ar. The resulting clusters are investigated by single photon ionization with tunable vacuum-ultraviolet synchrotron radiation and mass analyzed using reflectron mass spectrometry. Protonated methanol clusters of the form (CH3OH)nH+(n = 1-12) dominate the mass spectrum below the ionization energy of the methanol monomer. With an increase in water concentration, small amounts of mixed clusters of the form (CH3OH n(H2O)H+ (n = 2-11) are detected. The only unprotonated species observed in this work are the methanol monomer and dimer. Appearance energies are obtained from the photoionization efficiency (PIE) curves for CH3OH+, (CH3OH)2+, (CH3OH)nH+ (n = 1-9), and (CH3OH)n(H2O)H+ (n = 2-9) as a function of photon energy. With an increasein the water content in the molecular beam, there is an enhancement of photoionization intensity for the methanol dimer and protonated methanol monomer at threshold. These results are compared and contrasted to previous experimental observations.

  9. Vacuum-ultraviolet (VUV) photoionization of small methanol and methanol-water clusters

    SciTech Connect

    Ahmed, Musahid; Ahmed, Musahid; Wilson, Kevin R.; Belau, Leonid; Kostko, Oleg

    2008-05-12

    In this work we report on thevacuum-ultraviolet (VUV) photoionization of small methanol and methanol-water clusters. Clusters of methanol with water are generated via co-expansion of the gas phase constituents in a continuous supersonic jet expansion of methanol and water seeded in Ar. The resulting clusters are investigated by single photon ionization with tunable vacuumultraviolet synchrotron radiation and mass analyzed using reflectron mass spectrometry. Protonated methanol clusters of the form (CH3OH)nH + (n=1-12) dominate the mass spectrum below the ionization energy of the methanol monomer. With an increase in water concentration, small amounts of mixed clusters of the form (CH3OH)n(H2O)H + (n=2-11) are detected. The only unprotonated species observed in this work are the methanol monomer and dimer. Appearance energies are obtained from the photoionization efficiency (PIE) curves for CH3OH +, (CH 3OH)2 +, (CH3OH)nH + (n=1-9), and (CH 3OH)n(H2O)H + (n=2-9 ) as a function of photon energy. With an increase in the water content in the molecular beam, there is an enhancement of photoionization intensity for methanol dimer and protonated methanol monomer at threshold. These results are compared and contrasted to previous experimental observations.

  10. VUV photoionization of gas phase adenine and cytosine: A comparison between oven and aerosol vaporization

    NASA Astrophysics Data System (ADS)

    Touboul, D.; Gaie-Levrel, F.; Garcia, G. A.; Nahon, L.; Poisson, L.; Schwell, M.; Hochlaf, M.

    2013-03-01

    We studied the single photon ionization of gas phase adenine and cytosine by means of vacuum ultraviolet synchrotron radiation coupled to a velocity map imaging electron/ion coincidence spectrometer. Both in-vacuum temperature-controlled oven and aerosol thermodesorption were successfully applied to promote the intact neutral biological species into the gas phase. The photoion yields are consistent with previous measurements. In addition, we deduced the threshold photoelectron spectra and the slow photoelectron spectra for both species, where the close to zero kinetic energy photoelectrons and the corresponding photoions are measured in coincidence. The photoionization close and above the ionization energies are found to occur mainly via direct processes. Both vaporization techniques lead to similar electronic spectra for the two molecules, which consist of broadbands due to the complex electronic structure of the cationic species and to the possible contribution of several neutral tautomers for cytosine prior to ionization. Accurate ionization energies are measured for adenine and cytosine at, respectively, 8.267 ± 0.005 eV and 8.66 ± 0.01 eV, and we deduce precise thermochemical data for the adenine radical cation. Finally, we performed an evaluation and a comparison of the two vaporization techniques addressing the following criteria: measurement precision, thermal fragmentation, sensitivity, and sample consumption. The aerosol thermodesorption technique appears as a promising alternative to vaporize large thermolabile biological compounds, where extended thermal decomposition or low sensitivity could be encountered when using a simple oven vaporization technique.

  11. Internal energy selection in vacuum ultraviolet photoionization of ethanol and ethanol dimers.

    PubMed

    Bodi, Andras

    2013-10-14

    Internal energy selected ethanol monomer and ethanol dimer ions were prepared by threshold photoionization of a supersonic molecular beam seeded with ethanol. The dissociative photoionization processes of the monomer, the lowest-energy CH3-loss channel of the dimer, and the fragmentation of larger clusters were found to be disjunct from the ionization onset to about 12 eV, which made it possible to determine the 0 K appearance energy of C-C bond breaking in the H-donor unit of the ethanol dimer cation as 9.719 ± 0.004 eV. This reaction energy is used together with ab initio calculations in a thermochemical cycle to determine the binding energy change from the neutral ethanol dimer to a protonated ethanol-formaldehyde adduct. The cycle also shows general agreement between experiment, theory, and previously published enthalpies of formation. The role of the initial ionization site, or rather the initial photoion state, is also discussed based on the dimer breakdown diagram and excited state calculations. There is no evidence for isolated state behavior, and the ethanol dimer dissociative photoionization processes appear to be governed by statistical theory and the ground electronic state of the ion. In the monomer breakdown diagram, the smoothly changing branching ratio between H and CH3 loss is at odds with rate theory predictions, and shows that none of the currently employed few-parameter rate models, appropriate for experimental rate curve fitting, yields a correct description for this process in the experimental energy range.

  12. Absorption spectroscopy of a laboratory photoionized plasma experiment at Z

    SciTech Connect

    Hall, I. M.; Durmaz, T.; Mancini, R. C.; Bailey, J. E.; Rochau, G. A.; Golovkin, I. E.; MacFarlane, J. J.

    2014-03-15

    The Z facility at the Sandia National Laboratories is the most energetic terrestrial source of X-rays and provides an opportunity to produce photoionized plasmas in a relatively well characterised radiation environment. We use detailed atomic-kinetic and spectral simulations to analyze the absorption spectra of a photoionized neon plasma driven by the x-ray flux from a z-pinch. The broadband x-ray flux both photoionizes and backlights the plasma. In particular, we focus on extracting the charge state distribution of the plasma and the characteristics of the radiation field driving the plasma in order to estimate the ionisation parameter.

  13. Photoionization of optically trapped ultracold atoms with a high-power light-emitting diode

    SciTech Connect

    Goetz, Simone; Hoeltkemeier, Bastian; Amthor, Thomas; Weidemueller, Matthias

    2013-04-15

    Photoionization of laser-cooled atoms using short pulses of a high-power light-emitting diode (LED) is demonstrated. Light pulses as short as 30 ns have been realized with the simple LED driver circuit. We measure the ionization cross section of {sup 85}Rb atoms in the first excited state, and show how this technique can be used for calibrating efficiencies of ion detector assemblies.

  14. 4f photoionization and subsequent Auger decay in atomic Pb: Relativistic effects

    SciTech Connect

    Patanen, M.; Kantia, T.; Heinaesmaeki, S.; Aksela, S.; Aksela, H.; Urpelainen, S.

    2011-05-15

    High-resolution 4f photoelectron and subsequent Auger-electron spectra have been measured from free Pb atoms using synchrotron radiation. The fine structure of the spectra has been investigated theoretically by calculating the energies and intensities for 4f photoionization and Auger decay processes using the multiconfigurational Dirac-Fock approach. The role of the relativistic effects in the ground and singly and doubly ionized states has been studied on the basis of computed results and their comparison with experiment.

  15. Molecular imprinting sensor based on quantum weak measurement.

    PubMed

    Li, Dongmei; He, Qinghua; He, Yonghong; Xin, Meiguo; Zhang, Yilong; Shen, Zhiyuan

    2017-03-10

    A new type of sensing protocol, based on a high precision metrology of quantum weak measurement, was first proposed for molecularly imprinted polymers (MIP) sensor. The feasibility, sensitivity and selectivity of weak measurement based MIP (WMMIP) sensor were experimentally demonstrated with bovine serum albumin (BSA). Weak measurement system exhibits high sensitivity to the optical phase shift corresponding to the refractive index change, which is induced by the specific capture of target protein molecules with its recognition sites. The recognition process can be finally characterized by the central wavelength shift of output spectra through weak value amplification. In our experiment, we prepared BSA@MIP with modified reversed-phase microemulsion method, and coated it on the internal surface of measuring channels assembled into the Mach-Zehnder (MZ) interferometer based optical weak measurement system. The design of this home-built optical system makes it possible to detect analyte in real time. The dynamic process of the specific adsorption and concentration response to BSA from 5×10(-4) to 5×10(-1)μg/L was achieved with a limit of detection (LOD) of 8.01×10(-12)g/L. This WMMIP shows superiority in accuracy, fast response and low cost. Furthermore, real-time monitoring system can creatively promote the performance of MIP in molecular analysis.

  16. The Design and Measurement of Molecular Electronic Switches and Memories

    NASA Astrophysics Data System (ADS)

    Reed, Mark

    2000-03-01

    Electron transport studies in molecular-scale systems have recently become possible with the utilization of advanced microfabrication and self-assembly techniques. We have performed the measurement of the conductance of a single molecule using a break junction technique [1], the demonstration of molecular diodes [2], and the systematic investigation of metal-molecule contacts in a variety of systems [3]. Most recently, we have observed [4] large and useful reversible switching behavior in an electronic device that utilizes molecules as the active component, specifically a nitroamine redox center. The molecular device exhibits negative differential resistance (NDR) and peak-to-valley ratios exceeding 1000:1 and exceeds that observed in typical solid state quantum well resonant tunneling heterostructures. The designs of molecular switches, memories, and their circuit applications will be discussed. 1. M. A. Reed et al., Science 278, 252 (1997). 2. C. Zhou et al., Appl. Phys. Lett. 71, 611 (1997). 3. J. Chen et al., Chem Phys Lett 313, 741 (1999). 4. J. Chen et al., Science 286, 1550 (1999).

  17. Nondipole Effects in Double Photoionization of He

    SciTech Connect

    Istomin, A. Y.; Starace, A. F.; Manakov, N. L.; Meremianin, A. V.

    2006-01-09

    Lowest-order nondipole effects are studied in double photoionization (DPI) of the He atom. Ab initio parametrizations of the quadrupole transition amplitude for DPI from the 1S0-state are presented in terms of the exact two-electron reduced matrix elements. Parametrizations for the dipole-quadrupole triply differential cross section (TDCS) and doubly differential cross section (DDCS) are presented in terms of polarization-independent amplitudes for the case of an elliptically polarized photon. Expressions for the DDCS in terms of the reduced two-electron matrix elements are also given. A general analysis of retardation-induced asymmetries of the TDCS including the circular dichroism effect at equal energy sharing is presented. Our numerical results exhibit a nondipole forward-backward asymmetry in the TDCS for DPI of He at an excess energy of 450 eV that is in qualitative agreement with existing experimental data.

  18. Vacuum-Ultraviolet Photoionization and Mass Spectrometric Characterization of Lignin Monomers Coniferyl and Sinapyl Alcohols

    SciTech Connect

    Takahashi, Lynelle K.; Zhou, Jia; Kostko, Oleg; Golan, Amir; Leone, Stephen R.; Ahmed, Musahid

    2011-02-09

    The fragmentation mechanisms of monolignols under various energetic processes are studied with jet-cooled thermal desorption molecular beam (TDMB) mass spectrometry (MS), 25 keV Bi3+ secondary ion MS (SIMS), synchrotron vacuum-ultraviolet secondary neutral MS (VUV-SNMS) and theoretical methods. Experimental and calculated appearance energies of fragments observed in TDMB MS indicate that the coniferyl alcohol photoionization mass spectra contain the molecular parent and several dissociative photoionization products. Similar results obtained for sinapyl alcohol are also discussed briefly. Ionization energies of 7.60 eV ? 0.05 eV for coniferyl alcohol and<7.4 eV for both sinapyl and dihydrosinapyl alcohols are determined. The positive ion SIMS spectrum of coniferyl alcohol shares few characteristic peaks (m/z = 137 and 151) with the TDMB mass spectra, shows extensive fragmentation, and does not exhibit clear molecular parent signals. VUV-SNMS spectra, on the other hand, are dominated by the parent ion and main fragments also present in the TDMB spectra. Molecular fragmentation in VUV-SNMS spectra can be reduced by increasing the extraction delay time. Some features resembling the SIMS spectra are also observed in the desorbed neutral products. The monolignol VUV-SNMS peaks shared with the TDMB mass spectra suggest that dissociative photoionization of ion-sputtered neutral molecules predominate in the VUV-SNMS mass spectra, despite the extra internal energy imparted in the initial ion impact. The potential applications of these results to imaging mass spectrometry of bio-molecules are discussed.

  19. Dirac R-matrix calculations of photoionization cross-sections of Ca IV

    NASA Astrophysics Data System (ADS)

    Nazir, R. T.; Bari, M. A.; Sardar, S.; Bilal, M.; Salahuddin, M.; Nasim, M. H.

    2016-11-01

    In this paper total photoionization cross-sections in the ground (^2P^o_{3/2}) and two meta-stable states (^2P^o_{1/2},^2S_{1/2}) of Ca IV are reported using the relativistic Dirac Atomic R-matrix Codes (DARC) in the photon energy range 67-122 eV. The target wavefunctions are constructed with fully relativistic atomic structure GRASP package. A total of lowest lying 48 fine-structure levels arising from the four main configuration (3s23p4, 3s3p5 3s23p33d, 3p6) are considered for the target wavefunctions expansion. Our calculated eigenvalues of the core ion Ca V show reasonable agreement with available experimental and theoretical results. It is found that present ionization threshold energies of first three levels of Ca IV are in excellent agreement with NIST energies and experimental measurements. The photoionization cross-sections of Ca IV are calculated with an appropriate energy step (0.1 × 10-3 eV) to describe the resonance structures in vivid details. A comparison for the statistically weighted mixture of states (^2P^o_{3/2},^2P^o_{1/2}) with other experimental measurements including term-resolved ground state theoretical calculations is presented. Our computed photoionization cross-sections agree better with the measured cross-sections than the other theoretical approaches and are potentially more accurate.

  20. Recombination of polycyclic aromatic hydrocarbon photoions with electrons in a flowing afterglow plasma.

    PubMed

    Novotný, O; Sivaraman, B; Rebrion-Rowe, C; Travers, D; Biennier, L; Mitchell, J B A; Rowe, B R

    2005-09-08

    A new technique, flowing afterglow with photoions (FIAPI), has been developed to measure the rate coefficient for the recombination of complex ions, and, in particular, polycyclic aromatic hydrocarbon (PAH) cations with electrons. The method is based on the flowing afterglow Langmuir probe - mass spectrometer apparatus at the University of Rennes I. A helium plasma is generated by a microwave discharge in a He buffer gas and downstream, a small amount of argon gas is injected to destroy any helium metastables. A very small amount of neutral PAH molecules is added to the afterglow plasma by evaporation from a plate coated with the PAH to be studied. PAH ions are then produced by photoionization of the parent molecule using a pulsed UV laser (157 nm). The laser beam is oriented along the flow tube and so a constant spatial concentration of photoions is obtained. The electron concentration along the flow tube is measured by means of a movable Langmuir probe. Ion concentration decay in time is measured at a fixed position using a quadrupole mass spectrometer which is triggered by the laser pulse. The recombination of anthracene and pyrene cations has been studied using this technique and we have found a recombination rate of (2.4 +/- 0.8) x 10(-6) cm(3) s(-1) for anthracene and (4.1 +/- 1.2) x 10(-6) cm(3) s(-1) for pyrene.

  1. Recombination of polycyclic aromatic hydrocarbon photoions with electrons in a flowing afterglow plasma

    SciTech Connect

    Novotny, O.; Sivaraman, B.; Rebrion-Rowe, C.; Travers, D.; Biennier, L.; Mitchell, J.B.A.; Rowe, B.R.

    2005-09-08

    A new technique, flowing afterglow with photoions (FIAPI), has been developed to measure the rate coefficient for the recombination of complex ions, and, in particular, polycyclic aromatic hydrocarbon (PAH) cations with electrons. The method is based on the flowing afterglow Langmuir probe - mass spectrometer apparatus at the University of Rennes I. A helium plasma is generated by a microwave discharge in a He buffer gas and downstream, a small amount of argon gas is injected to destroy any helium metastables. A very small amount of neutral PAH molecules is added to the afterglow plasma by evaporation from a plate coated with the PAH to be studied. PAH ions are then produced by photoionization of the parent molecule using a pulsed UV laser (157 nm). The laser beam is oriented along the flow tube and so a constant spatial concentration of photoions is obtained. The electron concentration along the flow tube is measured by means of a movable Langmuir probe. Ion concentration decay in time is measured at a fixed position using a quadrupole mass spectrometer which is triggered by the laser pulse. The recombination of anthracene and pyrene cations has been studied using this technique and we have found a recombination rate of (2.4{+-}0.8)x10{sup -6} cm{sup 3} s{sup -1} for anthracene and (4.1{+-}1.2)x10{sup -6} cm{sup 3} s{sup -1} for pyrene.

  2. Recombination of polycyclic aromatic hydrocarbon photoions with electrons in a flowing afterglow plasma

    NASA Astrophysics Data System (ADS)

    Novotný, O.; Sivaraman, B.; Rebrion-Rowe, C.; Travers, D.; Biennier, L.; Mitchell, J. B. A.; Rowe, B. R.

    2005-09-01

    A new technique, flowing afterglow with photoions (FIAPI), has been developed to measure the rate coefficient for the recombination of complex ions, and, in particular, polycyclic aromatic hydrocarbon (PAH) cations with electrons. The method is based on the flowing afterglow Langmuir probe - mass spectrometer apparatus at the University of Rennes I. A helium plasma is generated by a microwave discharge in a He buffer gas and downstream, a small amount of argon gas is injected to destroy any helium metastables. A very small amount of neutral PAH molecules is added to the afterglow plasma by evaporation from a plate coated with the PAH to be studied. PAH ions are then produced by photoionization of the parent molecule using a pulsed UV laser (157 nm). The laser beam is oriented along the flow tube and so a constant spatial concentration of photoions is obtained. The electron concentration along the flow tube is measured by means of a movable Langmuir probe. Ion concentration decay in time is measured at a fixed position using a quadrupole mass spectrometer which is triggered by the laser pulse. The recombination of anthracene and pyrene cations has been studied using this technique and we have found a recombination rate of (2.4±0.8)×10-6cm3s-1 for anthracene and (4.1±1.2)×10-6cm3s-1 for pyrene.

  3. Selective detection of isomers with photoionization mass spectrometry for studies of hydrocarbon flame chemistry

    NASA Astrophysics Data System (ADS)

    Cool, Terrill A.; Nakajima, Koichi; Mostefaoui, Toufik A.; Qi, Fei; McIlroy, Andrew; Westmoreland, Phillip R.; Law, Matthew E.; Poisson, Lionel; Peterka, Darcy S.; Ahmed, Musahid

    2003-10-01

    We report the first use of synchrotron radiation, continuously tunable from 8 to 15 eV, for flame-sampling photoionization mass spectrometry (PIMS). Synchrotron radiation offers important advantages over the use of pulsed vacuum ultraviolet lasers for PIMS; these include superior signal-to-noise, soft ionization, and access to photon energies outside the limited tuning ranges of current VUV laser sources. Near-threshold photoionization efficiency measurements were used to determine the absolute concentrations of the allene and propyne isomers of C3H4 in low-pressure laminar ethylene-oxygen and benzene-oxygen flames. Similar measurements of the isomeric composition of C2H4O species in a fuel-rich ethylene-oxygen flame revealed the presence of substantial concentrations of ethenol (vinyl alcohol) and acetaldehyde. Ethenol has not been previously detected in hydrocarbon flames. Absolute photoionization cross sections were measured for ethylene, allene, propyne, and acetaldehyde, using propene as a calibration standard. PIE curves are presented for several additional reaction intermediates prominent in hydrocarbon flames.

  4. 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.

  5. Single-frequency 571nm VECSEL for photo-ionization of magnesium

    NASA Astrophysics Data System (ADS)

    Burd, S. C.; Leinonen, T.; Penttinen, J. P.; Allcock, D. T. C.; Slichter, D. H.; Srinivas, R.; Wilson, A. C.; Guina, M.; Leibfried, D.; Wineland, D. J.

    2016-06-01

    We report the development of an intracavity-frequency-doubled vertical external-cavity surface-emitting laser (VECSEL) emitting at 571 nm for photoionization of magnesium. The laser employs a V-cavity geometry with a gain chip at the end of one cavity arm and a lithium triborate (LBO) crystal for second harmonic generation. The gain chip has a bottom-emitting design with ten GaInAs quantum wells of 7 nm thickness, which are strain compensated by GaAsP. The system is capable of producing up to 2.4 +/- 0.1 W (total power in two separate output beams) in the visible. The free-running relative intensity noise was measured to be below -55 dBc/Hz over all frequencies from 1 Hz to 1 MHz. With acoustic isolation and temperature regulation of the laser breadboard, the mode-hop free operation time is typically over 5 hrs. To improve the long-term frequency stability, the laser can be locked to a Doppler-free transition of molecular iodine. To estimate the short-term linewidth, the laser was tuned to the resonance of a reference cavity. From analysis of the on-resonance Hänsch-Couillaud error signal we infer a linewidth of 50 +/- 10 kHz. Light at 285 nm is generated with an external build-up cavity containing a β-barium borate (BBO) crystal. The UV light is used for loading 25Mg+ ions in a surface-electrode RF Paul trap. These results demonstrate the applicability and versatility of high-power, single-frequency VECSELs with intracavity harmonic generation for applications in atomic and molecular physics.

  6. Direct identification of propargyl radical in combustion flames by vacuum ultraviolet photoionization mass spectrometry.

    PubMed

    Zhang, T; Tang, X N; Lau, K-C; Ng, C Y; Nicolas, C; Peterka, D S; Ahmed, M; Morton, Melita L; Ruscic, Branko; Yang, R; Wei, L X; Huang, C Q; Yang, B; Wang, J; Sheng, L S; Zhang, Y W; Qi, F

    2006-02-21

    We have developed an effusive laser photodissociation radical source, aiming for the production of vibrationally relaxed radicals. Employing this radical source, we have measured the vacuum ultraviolet (VUV) photoionization efficiency (PIE) spectrum of the propargyl radical (C(3)H(3)) formed by the 193 nm excimer laser photodissociation of propargyl chloride in the energy range of 8.5-9.9 eV using high-resolution (energy bandwidth = 1 meV) multibunch synchrotron radiation. The VUV-PIE spectrum of C(3)H(3) thus obtained is found to exhibit pronounced autoionization features, which are tentatively assigned as members of two vibrational progressions of C(3)H(3) in excited autoionizing Rydberg states. The ionization energy (IE = 8.674 +/- 0.001 eV) of C(3)H(3) determined by a small steplike feature resolved at the photoionization onset of the VUV-PIE spectrum is in excellent agreement with the IE value reported in a previous pulsed field ionization-photoelectron study. We have also calculated the Franck-Condon factors (FCFs) for the photoionization transitions C(3)H(3) (+)(X;nu(i),i = 1-12)<--C(3)H(3)(X). The comparison between the pattern of FCFs and the autoionization peaks resolved in the VUV-PIE spectrum of C(3)H(3) points to the conclusion that the resonance-enhanced autoionization mechanism is most likely responsible for the observation of pronounced autoionization features. We also present here the VUV-PIE spectra for the mass 39 ions observed in the VUV synchrotron-based photoionization mass spectrometric sampling of several premixed flames. The excellent agreement of the IE value and the pattern of autoionizing features of the VUV-PIE spectra observed in the photodissociation and flames studies has provided an unambiguous identification of the propargyl radical as an important intermediate in the premixed combustion flames. The discrepancy found between the PIE spectra obtained in flames and photodissociation at energies above the IE(C(3)H(3)) suggests that

  7. Two-Particle Coulomb Green Function Method with Projected Potential: Application to He Double Photoionization

    NASA Astrophysics Data System (ADS)

    Argenti, Luca; Colle, Renato

    2009-08-01

    A new method to compute fully differential double photoionization cross sections of atoms has been devised and fully developed for two-electron systems. The method exploits the Green function for two noninteracting electrons in the field of a nuclear charge to infer the effects of the residual potential projected on a set of L2-basis functions. Test calculations on helium at 100 eV excess energy indicate that, as long as the relevant part of the interaction potential is accounted for, the fully differential cross sections calculated in acceleration and velocity gauges converge in absolute value and reproduce measured angular distributions with a tunable accuracy. Generalization of the method to treat double photoionization of many-electron atoms is sketched.

  8. Two-particle coulomb Green function method with projected potential: application to He double photoionization.

    PubMed

    Argenti, Luca; Colle, Renato

    2009-12-31

    A new method to compute fully differential double photoionization cross sections of atoms has been devised and fully developed for two-electron systems. The method exploits the Green function for two noninteracting electrons in the field of a nuclear charge to infer the effects of the residual potential projected on a set of L(2)-basis functions. Test calculations on helium at 100 eV excess energy indicate that, as long as the relevant part of the interaction potential is accounted for, the fully differential cross sections calculated in acceleration and velocity gauges converge in absolute value and reproduce measured angular distributions with a tunable accuracy. Generalization of the method to treat double photoionization of many-electron atoms is sketched.

  9. Physical Mechanisms and Scaling Laws of K-Shell Double Photoionization

    SciTech Connect

    Hoszowska, J.; Dousse, J.-Cl.; Berset, M.; Cao, W.; Fennane, K.; Kayser, Y.; Szlachetko, J.; Szlachetko, M.; Kheifets, A. K.; Bray, I.; Kavcic, M.

    2009-02-20

    We report on the photon energy dependence of the K-shell double photoionization (DPI) of Mg, Al, and Si. The DPI cross sections were derived from high-resolution measurements of x-ray spectra following the radiative decay of the K-shell double vacancy states. Our data evince the relative importance of the final-state electron-electron interaction to the DPI. By comparing the double-to-single K-shell photoionization cross-section ratios for neutral atoms with convergent close-coupling calculations for He-like ions, the effect of outer shell electrons on the K-shell DPI process is assessed. Universal scaling of the DPI cross sections with the effective nuclear charge for neutral atoms is revealed.

  10. Physical Mechanisms and Scaling Laws of K-Shell Double Photoionization

    NASA Astrophysics Data System (ADS)

    Hoszowska, J.; Kheifets, A. K.; Dousse, J.-Cl.; Berset, M.; Bray, I.; Cao, W.; Fennane, K.; Kayser, Y.; Kavčič, M.; Szlachetko, J.; Szlachetko, M.

    2009-02-01

    We report on the photon energy dependence of the K-shell double photoionization (DPI) of Mg, Al, and Si. The DPI cross sections were derived from high-resolution measurements of x-ray spectra following the radiative decay of the K-shell double vacancy states. Our data evince the relative importance of the final-state electron-electron interaction to the DPI. By comparing the double-to-single K-shell photoionization cross-section ratios for neutral atoms with convergent close-coupling calculations for He-like ions, the effect of outer shell electrons on the K-shell DPI process is assessed. Universal scaling of the DPI cross sections with the effective nuclear charge for neutral atoms is revealed.

  11. Double K-shell photoionization of low-Z atoms and He-like ions

    NASA Astrophysics Data System (ADS)

    Hoszowska, J.; Kheifets, A. S.; Berset, M.; Bray, I.; Cao, W.; Dousse, J.-Cl.; Fennane, K.; Kavčič, M.; Kayser, Y.; Szlachetko, J.; Szlachetko, M.

    2009-03-01

    We report on the investigation of the photon energy dependence of double 1s photoionization of light atoms and compare the cross sections for hollow atom and He-like ion production. Measurements of the Kα hypersatellite x-ray spectra of Mg, Al, and Si were carried out using the Fribourg high-resolution x-ray spectrometer installed at the ID21 and ID26 beam lines at the ESRF. The double-to-single photoionization cross section ratios were derived as a function of the incident photon beam energy and compared to convergent close-coupling (CCC) calculations for He-like ions. The dynamical electron-electron scattering contribution to the DPI cross-sections was found to be more important for neutral atoms than for the He isoelectronic series.

  12. Density Functional study of Wigner-Smith time delays in photoionization and photorecombination of argon

    NASA Astrophysics Data System (ADS)

    Magrakvelidze, Maia; Madjet, Mohamed; Dixit, Gopal; Ivanov, Misha; Chakraborty, Himadri

    2015-05-01

    We investigate quantum phases and Wigner-Smith time delays in photoionization and photorecombination of valence electrons of argon using Kohn-Sham time-dependent local density approximation (TDLDA) with the Leeuwen and Baerends exchange-correlation functional. Numerical results for the phases at respective 3p and 3s Cooper minima show opposite variations resulting from the correlation that is based on mutual couplings between 3p and 3s channels. Computed attosecond Wigner-Smith time delays show excellent agreements with two recent independent experiments on argon that measured the relative 3s-3p time delay in photoionization and the delay in 3p photorecombination. This work was supported by the U.S. National Science Foundation.

  13. Radiation-magnetohydrodynamic simulations of the photoionization of magnetized globules

    NASA Astrophysics Data System (ADS)

    Henney, William J.; Arthur, S. Jane; de Colle, Fabio; Mellema, Garrelt

    2009-09-01

    We present the first three-dimensional radiation-magnetohydrodynamic simulations of the photoionization of a dense, magnetized molecular globule by an external source of ultraviolet radiation. We find that, for the case of a strong ionizing field, significant deviations from the non-magnetic evolution are seen when the initial magnetic field threading the globule has an associated magnetic pressure that is greater than 100 times the gas pressure. In such a strong-field case, the photoevaporating globule will adopt a flattened or `curled up' shape, depending on the initial field orientation, and magnetic confinement of the ionized photoevaporation flow can lead to recombination and subsequent fragmentation during advanced stages of the globule evolution. We find suggestive evidence that such magnetic effects may be important in the formation of bright, bar-like emission features in HII regions. We include simple but realistic fits to heating and cooling rates in the neutral and molecular gas in the vicinity of a high-mass star cluster, and show that the frequently used isothermal approximation can lead to an overestimate of the importance of gravitational instability in the radiatively imploded globule. For globules within 2 pc of a high-mass star cluster, we find that heating by stellar X-rays prevents the molecular gas from cooling below 50 K. Based in part on numerical simulations carried out using the Kan Balam supercomputer, operated by the Departamento de Supercómputo, Dirección General de Servicios de Cómputo Académico, Universidad Nacional Autónoma de México. E-mail: w.henney@astrosmo.unam.mx

  14. Photoionization of psoralen derivatives in micelles: Imperatorin and alloimperatorin

    NASA Astrophysics Data System (ADS)

    El-Gogary, Sameh R.

    2010-11-01

    The fluorescence properties of psoralen derivatives, 8-methoxypsoralen (8-MOP), imperatorin (IMP) and alloimperatorin (ALLOI), were investigated in various solvent and micellar solutions. The variation in intensity and maxima of the fluorescence in micellar solutions suggest that psoralens are located in the micelle-water interface region. Radical cations and hydrated electrons were generated by photoionization in micellar solution upon excitation at 266 nm. A nonlinear relationship between transient yield and photon fluency was obtained for each compound, indicating that a two-photon mechanism is predominant in the photoionization of the sensitizers. The photoionization efficiencies are significantly higher in anionic sodium dodecyl sulfate (SDS) than in cationic cetyltrimethylammonium bromide (CTAB) micelles, reflecting the influence of micelle charge on the efficiency of the separation of the photoproduced charge carriers. The photoionization efficiencies of IMP and ALLOI are similar.

  15. High-intensity photoionization of H sub 2

    SciTech Connect

    Allendorf, S.W.; Szoeke, A.

    1991-05-01

    A tunable, high-intensity picosecond dye laser system has been employed with electron energy analysis to investigate the dynamics of (3+1) resonance-enhanced multiphoton ionization of H{sub 2} via different vibrational levels of its B{sub 1}{Sigma}{sub u}{sup +} and C{sup 1}{Pi}{sub u} electronic states. We observe production of molecular ions in various vibrational levels, with a shift to increased population of lower vibrational states of H{sub 2}{sup +} consistent with the a.c. Stark shift of the correspondingly lower vibrational levels of the C state into resonance with the three- photon energy of the laser. Clear evidence of direct dissociation of H{sub 2} followed by single-photon ionization of the excited H atom is observed as well. Above threshold ionization of these two processes occurs readily. We also find that dissociative ionization is an increasingly important ionization pathway as the wavelength is increased. Finally, we see evidence of a new ionization pathway, which we assign to photoionization into a transient bound state created by the avoided crossing of the first repulsive electronic state of H{sub 2}{sup +}, {vert bar}2p{sigma}{sub u}, n{r angle}, with the single-photon-dressed ground state of H{sub 2}{sup +}, {vert bar}1s{sigma}{sub g},n + 1{r angle}. 6 refs., 2 figs.

  16. Photoionization of noble-gas atoms by ultrashort electromagnetic pulses

    SciTech Connect

    Astapenko, V. A. Svita, S. Yu.

    2014-11-15

    The photoionization of atoms of noble gases (Ar, Kr, and Xe) by ultrashort electromagnetic pulses of a corrected Gaussian shape is studied theoretically. Computations are performed in the context of perturbation theory using a simple expression for the total probability of photoionization of an atom by electromagnetic pulses. The features of this process are revealed and analyzed for various ranges of the parameters of the problem.

  17. CRF-PEPICO: Double velocity map imaging photoelectron photoion coincidence spectroscopy for reaction kinetics studies

    NASA Astrophysics Data System (ADS)

    Sztáray, Bálint; Voronova, Krisztina; Torma, Krisztián G.; Covert, Kyle J.; Bodi, Andras; Hemberger, Patrick; Gerber, Thomas; Osborn, David L.

    2017-07-01

    Photoelectron photoion coincidence (PEPICO) spectroscopy could become a powerful tool for the time-resolved study of multi-channel gas phase chemical reactions. Toward this goal, we have designed and tested electron and ion optics that form the core of a new PEPICO spectrometer, utilizing simultaneous velocity map imaging for both cations and electrons, while also achieving good cation mass resolution through space focusing. These optics are combined with a side-sampled, slow-flow chemical reactor for photolytic initiation of gas-phase chemical reactions. Together with a recent advance that dramatically increases the dynamic range in PEPICO spectroscopy [D. L. Osborn et al., J. Chem. Phys. 145, 164202 (2016)], the design described here demonstrates a complete prototype spectrometer and reactor interface to carry out time-resolved experiments. Combining dual velocity map imaging with cation space focusing yields tightly focused photoion images for translationally cold neutrals, while offering good mass resolution for thermal samples as well. The flexible optics design incorporates linear electric fields in the ionization region, surrounded by dual curved electric fields for velocity map imaging of ions and electrons. Furthermore, the design allows for a long extraction stage, which makes this the first PEPICO experiment to combine ion imaging with the unimolecular dissociation rate constant measurements of cations to detect and account for kinetic shifts. Four examples are shown to illustrate some capabilities of this new design. We recorded the threshold photoelectron spectrum of the propargyl and the iodomethyl radicals. While the former agrees well with a literature threshold photoelectron spectrum, we have succeeded in resolving the previously unobserved vibrational structure in the latter. We have also measured the bimolecular rate constant of the CH2I + O2 reaction and observed its product, the smallest Criegee intermediate, CH2OO. Finally, the second

  18. Optical measurement of transverse molecular diffusion in a microchannel.

    PubMed Central

    Kamholz, A E; Schilling, E A; Yager, P

    2001-01-01

    Quantitative analysis of molecular diffusion is a necessity for the efficient design of most microfluidic devices as well as an important biophysical method in its own right. This study demonstrates the rapid measurement of diffusion coefficients of large and small molecules in a microfluidic device, the T-sensor, by means of conventional epifluorescence microscopy. Data were collected by monitoring the transverse flux of analyte from a sample stream into a second stream flowing alongside it. As indicated by the low Reynolds numbers of the system (< 1), flow is laminar, and molecular transport between streams occurs only by diffusion. Quantitative determinations were made by fitting data with predictions of a one-dimensional model. Analysis was made of the flow development and its effect on the distribution of diffusing analyte using a three-dimensional modeling software package. Diffusion coefficients were measured for four fluorescently labeled molecules: fluorescein-biotin, insulin, ovalbumin, and streptavidin. The resulting values differed from accepted results by an average of 2.4%. Microfluidic system parameters can be selected to achieve accurate diffusion coefficient measurements and to optimize other microfluidic devices that rely on precise transverse transport of molecules. PMID:11259309

  19. Autoionization of molecular hydrogen: where do the Fano lineshapes go?

    PubMed

    Palacios, Alicia; Feist, Johannes; González-Castrillo, Alberto; Sanz-Vicario, José Luis; Martín, Fernando

    2013-05-10

    Atomic autoionization following photoabsorption is a typical example of quantum interferences governed by electron-electron correlation. Coherence between direct photoionization and autoionization paths results in "Fano profiles", widely explored in atoms in the last 60 years. The advent of femto- and attosecond laser technology made time-resolved images of the delayed electron ejection in autoionization accessible, leading to the reemergence of such studies in atomic systems. The counterpart molecular phenomena show the richness, as well as the complexity, added by nuclear motion, which may proceed on similar time scales. However, Fano profiles are usually absent in measured molecular photoionization cross sections and an unequivocal parametrization of molecular autoionization signatures, similar to that introduced by Fano in atoms [U. Fano, Phys. Rev. 1961, 124, 1866] has not yet been achieved. In this work we introduce a simple semiclassical model that accounts for all the features observed in H2 photoionization and demonstrate that the interference structures observed in dissociative ionization spectra are almost exclusively due to the phase accumulated in the nuclear motion. Furthermore, we show that the temporal build-up of these structures in the energy-differential cross sections is also determined by nuclear motion. We validate our models by comparing with full-dimensional ab initio calculations solving the time-dependent Schrödinger equation.

  20. Double photoionization of He and H{sub 2} at unequal energy sharing

    SciTech Connect

    Kheifets, A.S.; Bray, Igor

    2005-08-15

    A recently developed single-center model of double photoionization (DPI) of the H{sub 2} molecule [Kheifets, Phys. Rev. A 71, 022704 (2005)] has been extended to represent the DPI process at unequal energy sharing. The model is applied to describe the shape of the fully-differential cross-section (FDCS) of a randomly oriented hydrogen molecule in the isotopic form of D{sub 2} at the kinematics of recent experiments. Comparison with analogous FDCS for the He atom helps to elucidate the molecular effects.

  1. Evaluation of a hydrogen laser vacuum ultraviolet source for photoionization mass spectrometry of pharmaceuticals.

    PubMed

    Finch, Jeffrey W; Toerne, Kevin A; Schram, Karl H; Denton, M Bonner

    2005-01-01

    A photoionization hydrogen laser time-of-flight mass spectrometer system (H2-TOFMS) has been evaluated for the rapid analysis of drugs of abuse and pharmaceutical agents extracted from prescription tablets and spiked urine samples. The spectra obtained using the H2-TOFMS showed primarily intact molecular ions (M+*) after introduction by a heated probe and irradiation with vacuum ultraviolet (VUV) photons from the laser. Samples analyzed by this technique required only a simple solid-phase extraction step; no chromatographic separation or derivatization was necessary to identify the drugs of abuse or pharmaceutical agents.

  2. Determination of the absolute photoionization cross sections of CH3 and I produced from a pyrolysis source, by combined synchrotron and vacuum ultraviolet laser studies.

    PubMed

    Gans, Bérenger; Vieira Mendes, Luiz A; Boyé-Péronne, Séverine; Douin, Stéphane; Garcia, Gustavo; Soldi-Lose, Héloïse; Cunha de Miranda, Barbara K; Alcaraz, Christian; Carrasco, Nathalie; Pernot, Pascal; Gauyacq, Dolores

    2010-03-11

    A pyrolysis source coupled to a supersonic expansion has been used to produce the CH3 radical from two precursors, iodomethane CH3I and nitromethane CH3NO2. The relative ionization yield of CH3 has been recorded at the SOLEIL Synchrotron Radiation source in the range 9.0-11.6 eV, and its ionization threshold has been modeled by taking into account the vibrational and rotational temperature of the radical in the molecular beam. The relative photoionization yield has been normalized to an absolute cross section scale at a fixed wavelength (118.2 nm, sigma(i)(CH3) = 6.7(-1.8)(+2.4) Mb, 95% confidence interval) in an independent laboratory experiment using the same pyrolysis source, a vacuum ultraviolet (VUV) laser, and a carefully calibrated detection chain. The resulting absolute cross section curve is in good agreement with the recently published measurements by Taatjes et al., although with an improved signal-to-noise ratio. The absolute photoionization cross section of CH3I at 118.2 nm has also been measured to be sigma(i)(CH3I) = (48.2 +/- 7.9) Mb, in good agreement with previous electron impact measurements. Finally, the photoionization yield of the iodine atom in its ground state 2P(3/2) has been recorded using the synchrotron source and calibrated for the first time on an absolute cross section scale from our fixed 118.2 nm laser measurement, sigma(i)(I2P(3/2)) = 74(-23)(+33) Mb (95% confidence interval). The ionization curve of atomic iodine is in good agreement, although with slight variations, with the earlier relative ionization yield measured by Berkowitz et al. and is also compared to an earlier calculation of the iodine cross section by Robicheaux and Greene. It is demonstrated that, in the range of pyrolysis temperature used in this work, all the ionization cross sections are temperature-independent. Systematic care has been taken to include all uncertainty sources contributing to the final confidence intervals for the reported results.

  3. Comparison of measured and calculated thermospheric molecular oxygen densities

    NASA Technical Reports Server (NTRS)

    Potter, W. E.; Kayser, D. C.; Brinton, H. C.; Brace, L. H.; Oppenheimer, M.

    1977-01-01

    The open source neutral mass spectrometers on the AE-C, -D, and -E satellites were equipped with a 'fly-through' mode of operation which has provided direct measurements of molecular oxygen densities over a large portion of the globe. A complementary set of O2 densities is derived by using AE ion measurements and a scheme based on the daytime ion chemistry of O2(+) in the thermosphere. A comparison of the two data sets reveals general agreement over northern latitudes during periods of relatively low Ap and F10.7. The simplifying assumptions made in the photochemical scheme require that caution be used in calculating O2, especially at high latitudes and altitudes below 200 km

  4. Wind Measurements with a 355 nm Molecular Doppler Lidar

    NASA Technical Reports Server (NTRS)

    Gentry, Bruce M.; Chen, Huailin; Li, Steven X.

    2000-01-01

    A Doppler lidar system based on the molecular double edge technique is described. The system is mounted in a modified van to allow deployment in field operations. The lidar operates with a tripled Nd:YAG laser at 355 nm, a 45cm aperture telescope and a matching azimuth-over-elevation scanner to allow full sky access. Validated atmospheric wind profiles have been measured from 1.8 km to 35 km with a 178 m vertical resolution. The range dependent rms deviation of the horizontal wind speed is 0.4 - 6 m/s. The results of wind speed and direction are in good agreement with balloon sonde wind measurements made simultaneously at the same location.

  5. Comparison of measured and calculated thermospheric molecular oxygen densities

    NASA Technical Reports Server (NTRS)

    Potter, W. E.; Kayser, D. C.; Brinton, H. C.; Brace, L. H.; Oppenheimer, M.

    1977-01-01

    The open source neutral mass spectrometers on the AE-C, -D, and -E satellites were equipped with a 'fly-through' mode of operation which has provided direct measurements of molecular oxygen densities over a large portion of the globe. A complementary set of O2 densities is derived by using AE ion measurements and a scheme based on the daytime ion chemistry of O2(+) in the thermosphere. A comparison of the two data sets reveals general agreement over northern latitudes during periods of relatively low Ap and F10.7. The simplifying assumptions made in the photochemical scheme require that caution be used in calculating O2, especially at high latitudes and altitudes below 200 km

  6. The ionisation energy of cyclopentadienone: a photoelectron-photoion coincidence study

    NASA Astrophysics Data System (ADS)

    Ormond, Thomas K.; Hemberger, Patrick; Troy, Tyler P.; Ahmed, Musahid; Stanton, John F.; Ellison, G. Barney

    2015-08-01

    Imaging photoelectron photoion coincidence (iPEPICO) spectra of cyclopentadienone (C5H4=O and C5D4=O) have been measured at the Swiss Light Source Synchrotron (Paul Scherrer Institute, Villigen, Switzerland) at the Vacuum Ultraviolet (VUV) Beamline. Complementary to the photoelectron spectra, photoionisation efficiency curves were measured with tunable VUV radiation at the Chemical Dynamics Beamline at the Advanced Light Source Synchrotron (Lawrence Berkeley National Laboratory, Berkeley, CA, USA). For both experiments, molecular beams diluted in argon and helium were generated from the vacuum flash pyrolysis of o-phenylene sulphite in a resistively heated microtubular SiC flow reactor. The Franck-Condon profiles and ionisation energies were calculated at the CCSD(T) level of theory, and are in excellent agreement with the observed iPEPICO spectra. The ionisation energies of both cyclopentadienone-d0, IE(C5H4=O), and cyclopentadienone-d4, IE(C5D4=O), were observed to be the same: 9.41 ± 0.01 eV. The mass-selected threshold photoelectron spectrum (ms-TPES) of cyclopentadienone reveals that the C=C stretch in the ground state of the cation is excited upon ionisation, supporting computational evidence that the ground state of the cation is ? 2A2, and is in agreement with previous studies. However, the previously reported ionisation potential has been improved considerably in this work. In addition, since o-benzoquinone (o-O=C6H4=O and o-O=C6D4=O) is also produced in this process, its ms-TPES has been recorded. From the iPEPICO and photoionisation efficiency spectra, we infer an adiabatic ionisation energy of IE(o-O=C6H4=O) = 9.3 ± 0.1 eV, but the rather structureless spectrum indicates a strong change in geometry upon ionisation making this value less reliable.

  7. Anomalous Abundances in Gaseous Nebulae From Recombination and Collisional Lines: Improved Photoionization and Recombination Studies

    NASA Astrophysics Data System (ADS)

    Pradhan, Anil Kumar; Nahar, S. N.; Eissner, W. B.; Montenegro, M.

    2011-01-01

    A perplexing anomaly arises in the determination of abundances of common elements in gaseous nebulae, as derived from collisionally excited lines (CEL) as opposed to those from Recombination Lines (RCL). The "abundance discrepancy factors" can range from a factor of 2 to an order of magnitude or more. That has led to quite different interpretation of the physical structure and processes in gaseous nebulae, such as temperature fluctuations across the object, or metal-rich concentrations leading to a dual-abundnace scenario. We show that the problem may lie in inaccuracies in photoionization and recombination models neglecting low-energy resonance phenomena due to fine structure. Whereas the atomic physics of electron impact excitation of forbidden lines is well understood, and accurate collision strengths have long been available, that is not generally the case for electron-ion recombination cross sections. A major problem is the inclusion of relativisitic effects as it pertains to the existence of very low-energy fine structure resonances in photoionization cross sections. We carry out new relativistic calculations for photoionization and recombination cross sections using a recently extended version of the Breit-Pauli R-matrix codes, and the unified electron-ion recombination method that subsumes both the radiative and the dielectronic recombination (RR and DR) processes in an ab initio and self-consistent manner. We find that near-thresold resonances manifest themselves within fine structure levels of the ground state of ions, enhancing low-temperature recombination rate coefficients at 1000-10,000 K. The resulting enahncement in level-specific and total recombination rate coefficients should therefore lead to reduced abundances derived from RCL, and in accordance with those from CEL. We present results for photoionization of O II into, and recombination from, O III. Theoretical cross sections are benchmarked against high-resolution measurements from synchrotron

  8. Spectral dependence of nanocrystal photoionization probability: the role of hot-carrier transfer.

    PubMed

    Padilha, Lazaro A; Robel, István; Lee, Doh C; Nagpal, Prashant; Pietryga, Jeffrey M; Klimov, Victor I

    2011-06-28

    We conduct measurements of photocharging of PbSe and PbS nanocrystal quantum dots (NQDs) as a function of excitation energy (ℏω). We observe a rapid growth of the degree of photocharging with increasing ℏω, which indicates an important role of hot-carrier transfer in the photoionization process. The corresponding spectral dependence exhibits two thresholds that mark the onsets of weak and strong photocharging. Interestingly, both thresholds are linked to the NQD band gap energy (E(g)) and scale as ∼1.5E(g) and ∼3E(g), indicating that the onsets of photoionization are associated with specific nanocrystal states (tentatively, 1P and 2P, respectively) and are not significantly dependent on the energy of external acceptor sites. For all samples, the hot-electron transfer probability increases by nearly 2 orders of magnitude as photon energy increases from 1.5 to 3.5 eV, although at any given wavelength the photoionization probability shows significant sample-to-sample variations (∼10(-6) to 10(-3) for 1.5 eV and ∼10(-4) to 10(-1) for 3.5 eV). In addition to the effect of the NQD size, these variations are likely due to differences in the properties of the NQD surface and/or the number and identity of external acceptor trap sites. The charge-separated states produced by photoionization are characterized by extremely long lifetimes (20 to 85 s) that become longer with increasing NQD size.

  9. Conformation-specific dissociative photoionization of oxalyl chloride in the gas phase

    NASA Astrophysics Data System (ADS)

    Chu, Genbai; Chen, Jun; Liu, Fuyi; Shan, Xiaobin; Han, Juguang; Sheng, Liusi

    2013-04-01

    The photoionization and photodissociation of oxalyl chloride have been studied by synchrotron vacuum ultraviolet (VUV) photoionization mass spectrometry. The ionization energy of C2Cl2O2 (10.91 ± 0.05 eV) and appearance energies (AEs) for fragment ions CCl2O+, CClO2+, CClO+, CO2+, CO2+, and Cl+ from C2Cl2O2 have been measured from the photoionization efficiency (PIE) spectra. In addition, three conformers of CClO2+ ion, namely trans-, gauche- and cis-conformer are investigated by using CBS-QB3 and W1u methods, which suggest that the existence of the cis-conformation parent ion CClO2+ is consistent with the second onset at 11.6 eV in the experimental PIE curve and the associated calculations. The formation channels of fragment ions near the ionization thresholds are discussed by means of CBS-QB3 and W1u calculated results and thermochemistry results. The dominant fragment ion CClO+ is mainly originated from direct cleavage of the elongated C-C bond in the trans-conformer parent ion after ionization. The calculated results are in good agreement with the experimental data.

  10. State-to-State Spectroscopy and Dynamics of Ions and Neutrals by Photoionization and Photoelectron Methods

    NASA Astrophysics Data System (ADS)

    Ng, Cheuk-Yiu

    2014-04-01

    Recent advances in high-resolution photoionization, photoelectron, and photodissociation studies based on single-photon vacuum ultraviolet (VUV) and two-color infrared (IR)-VUV, visible (Vis)-ultraviolet (UV), and VUV-VUV laser excitations are illustrated with selected examples. VUV laser photoionization coupled with velocity-map-imaging threshold photoelectron (VMI-TPE) detection can achieve comparable energy resolution but has higher-detection sensitivities than those observed in VUV laser pulsed field ionization photoelectron (PFI-PE) measurements. For molecules with known intermediate states, IR-VUV and Vis-UV excitation schemes are highly sensitive for rovibronically selected and resolved PFI-PE studies. The successful applications of the VUV-PFI-PE, VUV-VMI-TPE, and Vis-UV-PFI-PE methods to state-resolved and state-to-state photoelectron studies of transient radicals and transitional metal-containing molecules are highlighted. The most recently established VUV-VUV pump-probe time-slice VMI photoion method is shown to be promising for state-to-state photodissociation studies of small molecules relevant to planetary atmospheres and for the fundamental understanding of photodissociation dynamics.

  11. State-To Spectroscopy and Dynamics of Ions and Neutrals by Photoionization and Photoelectron Methods

    NASA Astrophysics Data System (ADS)

    Ng, Cheuk-Yiu

    2014-06-01

    Recent advances in high-resolution photoionization, photoelectron, and photodissociation studies based on single-photon vacuum ultraviolet (VUV) and two-color infrared (IR)-VUV, visible (VIS)-ultraviolet (UV), and VUV-VUV laser excitations are illustrated with selected examples. We show that VUV laser photoionization coupled with velocity-map-imaging (VMI)-threshold photoelectron (VMI-TPE) detection can achieve comparable energy resolutions, but higher detection sensitivities than those observed in VUV laser pulsed field ionization-photoelectron (PFI-PE) measurements. For molecules with known intermediate states, IR-VUV and VIS-UV excitation schemes are highly sensitive for rovibronically selected and resolved PFI-PE studies. The successful applications of the VUV-PFI-PE, VUV-VMI-TPE and VIS-UV-PFI-PE methods to state-resolved and state-to-state photoelectron studies of transient radicals and transitional metal-containing molecules are highlighted. The most recently established VUV-VUV pump-probe time-slice VMI-photoion method is shown to be promising for state-to-state photodissociation studies of small molecules relevant to planetary atmospheres and for the fundamental understanding of photodissociation dynamics.

  12. Grafting of Ring-Opened Cyclopropylamine Thin Films on Silicon (100) Hydride via UV Photoionization.

    PubMed

    Tung, J; Ching, J Y; Ng, Y M; Tew, L S; Khung, Y L

    2017-08-31

    The grafting of cyclopropylamine onto a silicon (100) hydride (Si-H) surface via a ring-opening mechanism using UV photoionization is described here. In brief, radicals generated from the Si-H surface upon UV irradiation were found to behave in classical hydrogen abstraction theory manner by which the distal amine group was first hydrogen abstracted and the radical propagated down to the cyclopropane moiety. This subsequently liberated the strained bonds of the cyclopropane group and initiated the surface grafting process, producing a thin film approximately 10-15 nm in height. Contact angle measurements also showed that such photoionization irradiation had yielded an extremely hydrophilic surface (∼21.3°) and X-ray photoelectron spectroscopy also confirmed the coupling was through the Si-C linkage. However, when the surface underwent high-temperature hydrosilylation (>160 °C), the reaction proceeded predominantly through the nucleophilic NH2 group to form a Si-N linkage to the surface. This rendered the surface hydrophobic and hence suggested that the Si-H homolysis model may not be the main process. To the best of our knowledge, this was the first attempt reported in the literature to use photoionization to directly graft cyclopropylamine onto a silicon surface and in due course generate a highly rich NH-terminated surface that was found to be highly bioactive in promoting cell viability on the basis of 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide studies.

  13. State-to-state spectroscopy and dynamics of ions and neutrals by photoionization and photoelectron methods.

    PubMed

    Ng, Cheuk-Yiu

    2014-01-01

    Recent advances in high-resolution photoionization, photoelectron, and photodissociation studies based on single-photon vacuum ultraviolet (VUV) and two-color infrared (IR)-VUV, visible (Vis)-ultraviolet (UV), and VUV-VUV laser excitations are illustrated with selected examples. VUV laser photoionization coupled with velocity-map-imaging threshold photoelectron (VMI-TPE) detection can achieve comparable energy resolution but has higher-detection sensitivities than those observed in VUV laser pulsed field ionization photoelectron (PFI-PE) measurements. For molecules with known intermediate states, IR-VUV and Vis-UV excitation schemes are highly sensitive for rovibronically selected and resolved PFI-PE studies. The successful applications of the VUV-PFI-PE, VUV-VMI-TPE, and Vis-UV-PFI-PE methods to state-resolved and state-to-state photoelectron studies of transient radicals and transitional metal-containing molecules are highlighted. The most recently established VUV-VUV pump-probe time-slice VMI photoion method is shown to be promising for state-to-state photodissociation studies of small molecules relevant to planetary atmospheres and for the fundamental understanding of photodissociation dynamics.

  14. Photoionization study of L-valine in the gas phase by vacuum ultraviolet synchrotron radiation.

    PubMed

    Zhou, Shaohui; Chu, Genbai; Cao, Lanlan; Shan, Xiaobin; Liu, Fuyi; Han, Ju-Guang; Sheng, Liusi

    2011-01-01

    The photoionization and photodissociation of L-valine are studied by tunable synchrotron vacuum ultraviolet photoionization mass spectrometry at the photon energy of 13 eV. The ionization energy of L-valine and the appearance energies of major fragments are measured by the photoionization efficiency spectrum in the photon energy range of 8-11 eV. Possible formation pathways of the major fragments, NH(2)CHC(OH)(2)(+) (m/z=75), NH(2)(CH(3))(2)(CH)(2)(+) (m/z=72) and NH(2)CHCO(+) (m/z=57), are discussed in detail with the theoretical calculations at the B3LYP/6-31++G (d, p) level. Hydrogen migration is considered as the key way for the formation of NH(2)CHC(OH)(2)(+) (m/z=75) and NH(2)CHCO(+) (m/z=57). Furthermore, other fragments, NH(2)CHCOOH(+) (m/z=74), (CH(3))(2)(CH)(2)(+) (m/z=56), C(4)H(7)(+) (m/z=55), NH(2)CHOH(+) (m/z=46), NH(2)CH(2)(+) (m/z=30) and m/z=18, species are also briefly described.

  15. Theoretical treatment of double photoionization of helium using a B-spline implementation of exterior complex scaling

    SciTech Connect

    McCurdy, C. William; Horner, Daniel A.; Rescigno, Thomas N.; Martin, Fernando

    2004-02-19

    Calculations of absolute triple differential and single differential cross sections for helium double photoionization are performed using an implementation of exterior complex scaling in B-splines. Results for cross sections, well-converged in partial waves, are presented and compared with both experiment and earlier theoretical calculations. These calculations establish the practicality and effectiveness of the complex B-spline approach to calculations of double ionization of atomic and molecular systems.

  16. Experimental absolute cross section for photoionization of Xe^7+

    NASA Astrophysics Data System (ADS)

    Schippers, S.; Müller, A.; Esteves, D.; Habibi, M.; Aguilar, A.; Kilcoyne, A. L. D.

    2010-03-01

    Collision processes with highly charged xenon ions are of interest for UV-radiation generation in plasma discharges, for fusion research and for space craft propulsion. Here we report results for the photoionization of Xe^7+ ionsootnotetextS. Schippers et al., J. Phys.: Conf. Ser. (in print) which were measured at the photon-ion end station of ALS beamline 10.0.1. As compared with the only previous experimental studyootnotetextJ. M. Bizau et al., Phys. Rev. Lett. 84, 435 (2000) of this reaction, the present cross sections were obtained at higher energy resolution (50--80 meV vs. 200--500 meV) and on an absolute cross section scale. In the experimental photon energy range of 95--145 eV the cross section is dominated by resonances associated with 4d->5f excitation and subsequent autoionization. The most prominent feature in the measured spectrum is the 4d^9,s,f, resonance at 121.14±0.02 eV which reaches a peak cross section of 1.2 Gb at 50 meV photon energy spread. The experimental resonance strength of 160 Mb eV (corresponding to an absorption oscillator strength of 1.46) is in fair agreement with the theoretical result^2.

  17. Photo-ionized lithium source for plasma accelerator applications

    SciTech Connect

    Muggli, P. . Dept. of Electrical Engineering Univ. of Southern California, Los Angeles, CA . Dept. of Electrical Engineering and Quantum Electronics); Marsh, K.A.; Wang, S.; Clayton, C.E.; Joshi, C. . Dept. of Electrical Engineering); Lee, S.; Katsouleas, T.C. . Dept. of Electrical Engineering and Quantum Electronics)

    1999-06-01

    A photo-ionized lithium source is developed for plasma acceleration applications. A homogeneous column of lithium neutral vapor with a density of 2 [times] 10[sup 15] cm[sup [minus]3] is confined by helium gas in a heat-pipe oven. A UV laser pulse ionizes the vapor. In this device, the length of the neutral vapor and plasma column is 25 cm. The plasma density was measured by laser interferometry in the visible on the lithium neutrals and by CO[sub 2] laser interferometry on the plasma electrons. The maximum measured plasma density was 2.9 [times] 10[sup 14] cm[sup [minus]3], limited by the available UV fluence ([approx]83 mJ/cm[sup 2]), corresponding to a 15% ionization fraction. After ionization, the plasma density decreases by a factor of two in about 12 [micro]s. These results show that such a plasma source is scaleable to lengths of the order of 1 m and should satisfy all the requirements for demonstrating the acceleration of electrons by 1 GeV in a 1-GeV/m amplitude plasma wake.

  18. Vacuum ultraviolet photoionization of carbohydrates and nucleotides

    SciTech Connect

    Shin, Joong-Won; Bernstein, Elliot R.

    2014-01-28

    Carbohydrates (2-deoxyribose, ribose, and xylose) and nucleotides (adenosine-, cytidine-, guanosine-, and uridine-5{sup ′}-monophosphate) are generated in the gas phase, and ionized with vacuum ultraviolet photons (VUV, 118.2 nm). The observed time of flight mass spectra of the carbohydrate fragmentation are similar to those observed [J.-W. Shin, F. Dong, M. Grisham, J. J. Rocca, and E. R. Bernstein, Chem. Phys. Lett. 506, 161 (2011)] for 46.9 nm photon ionization, but with more intensity in higher mass fragment ions. The tendency of carbohydrate ions to fragment extensively following ionization seemingly suggests that nucleic acids might undergo radiation damage as a result of carbohydrate, rather than nucleobase fragmentation. VUV photoionization of nucleotides (monophosphate-carbohydrate-nucleobase), however, shows that the carbohydrate-nucleobase bond is the primary fragmentation site for these species. Density functional theory (DFT) calculations indicate that the removed carbohydrate electrons by the 118.2 nm photons are associated with endocyclic C–C and C–O ring centered orbitals: loss of electron density in the ring bonds of the nascent ion can thus account for the observed fragmentation patterns following carbohydrate ionization. DFT calculations also indicate that electrons removed from nucleotides under these same conditions are associated with orbitals involved with the nucleobase-saccharide linkage electron density. The calculations give a general mechanism and explanation of the experimental results.

  19. Cooling and Heating Functions of Photoionized Gas

    NASA Astrophysics Data System (ADS)

    Gnedin, Nickolay Y.; Hollon, Nicholas

    2012-10-01

    Cooling and heating functions of cosmic gas are crucial ingredients for any study of gas dynamics and thermodynamics in the interstellar and intergalactic media. As such, they have been studied extensively in the past under the assumption of collisional ionization equilibrium. However, for a wide range of applications, the local radiation field introduces a non-negligible, often dominant, modification to the cooling and heating functions. In the most general case, these modifications cannot be described in simple terms and would require a detailed calculation with a large set of chemical species using a radiative transfer code (the well-known code Cloudy, for example). We show, however, that for a sufficiently general variation in the spectral shape and intensity of the incident radiation field, the cooling and heating functions can be approximated as depending only on several photoionization rates, which can be thought of as representative samples of the overall radiation field. This dependence is easy to tabulate and implement in cosmological or galactic-scale simulations, thus economically accounting for an important but rarely included factor in the evolution of cosmic gas. We also show a few examples where the radiation environment has a large effect, the most spectacular of which is a quasar that suppresses gas cooling in its host halo without any mechanical or non-radiative thermal feedback.

  20. Intergalactic magnetogenesis at Cosmic Dawn by photoionization

    NASA Astrophysics Data System (ADS)

    Durrive, J.-B.; Langer, M.

    2015-10-01

    We present a detailed analysis of an astrophysical mechanism that generates cosmological magnetic fields during the Epoch of Reionization. It is based on the photoionization of the intergalactic medium by the first sources formed in the Universe. First the induction equation is derived, then the characteristic length and time-scales of the mechanism are identified, and finally numerical applications are carried out for first stars, primordial galaxies and distant powerful quasars. In these simple examples, the strength of the generated magnetic fields varies between the order of 10-23 G on hundreds of kiloparsecs and 10-19 G on hundreds of parsecs in the neutral intergalactic medium between the Strömgren spheres of the sources. Thus, this mechanism contributes to the premagnetization of the whole Universe before large-scale structures are in place. It operates with any ionizing source, at any time during the Epoch of Reionization. Finally, the generated fields possess a characteristic spatial configuration which may help discriminate these seeds from those produced by different mechanisms.

  1. Vacuum ultraviolet photoionization of carbohydrates and nucleotides

    NASA Astrophysics Data System (ADS)

    Shin, Joong-Won; Bernstein, Elliot R.

    2014-01-01

    Carbohydrates (2-deoxyribose, ribose, and xylose) and nucleotides (adenosine-, cytidine-, guanosine-, and uridine-5'-monophosphate) are generated in the gas phase, and ionized with vacuum ultraviolet photons (VUV, 118.2 nm). The observed time of flight mass spectra of the carbohydrate fragmentation are similar to those observed [J.-W. Shin, F. Dong, M. Grisham, J. J. Rocca, and E. R. Bernstein, Chem. Phys. Lett. 506, 161 (2011)] for 46.9 nm photon ionization, but with more intensity in higher mass fragment ions. The tendency of carbohydrate ions to fragment extensively following ionization seemingly suggests that nucleic acids might undergo radiation damage as a result of carbohydrate, rather than nucleobase fragmentation. VUV photoionization of nucleotides (monophosphate-carbohydrate-nucleobase), however, shows that the carbohydrate-nucleobase bond is the primary fragmentation site for these species. Density functional theory (DFT) calculations indicate that the removed carbohydrate electrons by the 118.2 nm photons are associated with endocyclic C-C and C-O ring centered orbitals: loss of electron density in the ring bonds of the nascent ion can thus account for the observed fragmentation patterns following carbohydrate ionization. DFT calculations also indicate that electrons removed from nucleotides under these same conditions are associated with orbitals involved with the nucleobase-saccharide linkage electron density. The calculations give a general mechanism and explanation of the experimental results.

  2. Short-time dynamics of molecular junctions after projective measurement

    NASA Astrophysics Data System (ADS)

    Tang, Gaomin; Xing, Yanxia; Wang, Jian

    2017-08-01

    In this work, we study the short-time dynamics of a molecular junction described by Anderson-Holstein model using full-counting statistics after projective measurement. The coupling between the central quantum dot (QD) and two leads was turned on at remote past and the system is evolved to steady state at time t =0 , when we perform the projective measurement in one of the lead. Generating function for the charge transfer is expressed as a Fredholm determinant in terms of Keldysh nonequilibrium Green's function in the time domain. It is found that the current is not constant at short times indicating that the measurement does perturb the system. We numerically compare the current behaviors after the projective measurement with those in the transient regime where the subsystems are connected at t =0 . The universal scaling for high-order cumulants is observed for the case with zero QD occupation due to the unidirectional transport at short times. The influences of electron-phonon interaction on short-time dynamics of electric current, shot noise, and differential conductance are analyzed.

  3. A High-resolution Vacuum Ultraviolet Laser Photoionization and Photoelectron Study of the Co Atom

    NASA Astrophysics Data System (ADS)

    Huang, Huang; Wang, Hailing; Luo, Zhihong; Shi, Xiaoyu; Chang, Yih-Chung; Ng, C. Y.

    2016-12-01

    We have measured the vacuum ultraviolet-photoionization efficiency (VUV-PIE) spectrum of Co in the energy range of 63,500-67,000 cm-1, which covers the photoionization transitions of Co(3d74s2 4F9/2) \\to Co+(3d8 3F4), Co(3d74s2 4F7/2) \\to Co+(3d8 3F3), Co(3d74s2 4F9/2) \\to Co+(3d8 3F3), Co(3d74s2 4F9/2) \\to Co+(3d8 3F2), and Co(3d74s2 4F9/2) \\to Co+(3d74s1 5F5). We have also recorded the pulsed field ionization photoelectron spectrum of Co in the same energy range, allowing accurate determinations of ionization energies (IEs) for the photoionization transitions from the Co(3d74s2 4F9/2) ground neutral state to the Co+(3F J ) (J = 4 and 3) and Co+(5F5) ionic states, as well as from the Co(3d74s2 4F7/2) excited neural state to the Co+(3d8 3F3) ionic state. The high-resolution nature of the VUV laser used has allowed the observation of many well-resolved autoionizing resonances in the VUV-PIE spectrum, among which an autoionizing Rydberg series, 3d74s1(5F5)np (n = 19-38), converging to the Co+(3d74s1 5F5) ionic state from the Co(3d74s2 4F9/2) ground neutral state is identified. The fact that no discernible step-like structures are present at these ionization thresholds in the VUV-PIE spectrum indicates that direct photoionization of Co is minor compared to autoionization in this energy range. The IE values, the autoionizing Rydberg series, and the photoionization cross sections obtained in this experiment are valuable for understanding the VUV opacity and abundance measurement of the Co atom in stars and solar atmospheres, as well as for benchmarking the theoretical results calculated in the Opacity Project and the IRON Project, and thus are of relevance to astrophysics.

  4. Contact potential difference measurements of doped organic molecular thin films

    NASA Astrophysics Data System (ADS)

    Chan, Calvin; Gao, Weiying; Kahn, Antoine

    2004-07-01

    The possibility of nonequilibrium conditions in doped organic molecular thin films is investigated using a combination of ultraviolet photoemission spectroscopy (UPS) and contact potential difference measurements. Surface or interface photovoltage is of particular concern in materials with large band gap and appreciable band (or energy level) bending at interfaces. We investigate here zinc phthalocyanine (ZnPc) and N,N'-diphenyl-N,N'-bis(1-naphthyl)-1,1'biphenyl-4,4'' diamine (α-NPD) p-doped with the acceptor molecule, tetrafluorotetracyanoquinodimethane (F4-TCNQ). In both cases, we observe an upward movement of the vacuum level away from the metal interface with respect to the Fermi level, consistent with the formation of a depletion region. We show that photovoltage is not a significant factor in these doped films, under ultraviolet illumination during UPS. We suggest that the carrier recombination rate in organic films is sufficiently fast to exclude any photovoltage effects at room temperature. .

  5. Quantitative estimates of precision for molecular isotopic measurements.

    PubMed

    Jasper, J P

    2001-01-01

    At least three methods of calculating the random errors or variance of molecular isotopic data are presently in use. The major components of variance are differentiated and quantified here into least three to four individual components. The measurement of error of the analyte relative to a working (whether an internal or an external) standard is quantified via the statistical pooled estimate of error. A statistical method for calculating the total variance associated with the difference of two individual isotopic compositions from two isotope laboratories is given, including the variances of the laboratory (secondary) and working standards, as well as those of the analytes. An abbreviated method for estimation of of error typical for chromatographic/isotope mass spectrometric methods is also presented. Copyright 2001 John Wiley & Sons, Ltd.

  6. Chasing charge localization and chemical reactivity following photoionization in liquid water

    NASA Astrophysics Data System (ADS)

    Marsalek, Ondrej; Elles, Christopher G.; Pieniazek, Piotr A.; Pluhařová, Eva; VandeVondele, Joost; Bradforth, Stephen E.; Jungwirth, Pavel

    2011-12-01

    The ultrafast dynamics of the cationic hole formed in bulk liquid water following ionization is investigated by ab initio molecular dynamics simulations and an experimentally accessible signature is suggested that might be tracked by femtosecond pump-probe spectroscopy. This is one of the fastest fundamental processes occurring in radiation-induced chemistry in aqueous systems and biological tissue. However, unlike the excess electron formed in the same process, the nature and time evolution of the cationic hole has been hitherto little studied. Simulations show that an initially partially delocalized cationic hole localizes within ˜30 fs after which proton transfer to a neighboring water molecule proceeds practically immediately, leading to the formation of the OH radical and the hydronium cation in a reaction which can be formally written as H2O+ + H2O → OH + H3O+. The exact amount of initial spin delocalization is, however, somewhat method dependent, being realistically described by approximate density functional theory methods corrected for the self-interaction error. Localization, and then the evolving separation of spin and charge, changes the electronic structure of the radical center. This is manifested in the spectrum of electronic excitations which is calculated for the ensemble of ab initio molecular dynamics trajectories using a quantum mechanics/molecular mechanics (QM/MM) formalism applying the equation of motion coupled-clusters method to the radical core. A clear spectroscopic signature is predicted by the theoretical model: as the hole transforms into a hydroxyl radical, a transient electronic absorption in the visible shifts to the blue, growing toward the near ultraviolet. Experimental evidence for this primary radiation-induced process is sought using femtosecond photoionization of liquid water excited with two photons at 11 eV. Transient absorption measurements carried out with ˜40 fs time resolution and broadband spectral probing across

  7. Chasing charge localization and chemical reactivity following photoionization in liquid water.

    PubMed

    Marsalek, Ondrej; Elles, Christopher G; Pieniazek, Piotr A; Pluhařová, Eva; VandeVondele, Joost; Bradforth, Stephen E; Jungwirth, Pavel

    2011-12-14

    The ultrafast dynamics of the cationic hole formed in bulk liquid water following ionization is investigated by ab initio molecular dynamics simulations and an experimentally accessible signature is suggested that might be tracked by femtosecond pump-probe spectroscopy. This is one of the fastest fundamental processes occurring in radiation-induced chemistry in aqueous systems and biological tissue. However, unlike the excess electron formed in the same process, the nature and time evolution of the cationic hole has been hitherto little studied. Simulations show that an initially partially delocalized cationic hole localizes within ~30 fs after which proton transfer to a neighboring water molecule proceeds practically immediately, leading to the formation of the OH radical and the hydronium cation in a reaction which can be formally written as H(2)O(+) + H(2)O → OH + H(3)O(+). The exact amount of initial spin delocalization is, however, somewhat method dependent, being realistically described by approximate density functional theory methods corrected for the self-interaction error. Localization, and then the evolving separation of spin and charge, changes the electronic structure of the radical center. This is manifested in the spectrum of electronic excitations which is calculated for the ensemble of ab initio molecular dynamics trajectories using a quantum mechanics/molecular mechanics (QM∕MM) formalism applying the equation of motion coupled-clusters method to the radical core. A clear spectroscopic signature is predicted by the theoretical model: as the hole transforms into a hydroxyl radical, a transient electronic absorption in the visible shifts to the blue, growing toward the near ultraviolet. Experimental evidence for this primary radiation-induced process is sought using femtosecond photoionization of liquid water excited with two photons at 11 eV. Transient absorption measurements carried out with ~40 fs time resolution and broadband spectral probing

  8. Chasing charge localization and chemical reactivity following photoionization in liquid water

    SciTech Connect

    Marsalek, Ondrej; Pluharova, Eva; Jungwirth, Pavel; Elles, Christopher G.; Pieniazek, Piotr A.; Bradforth, Stephen E.; VandeVondele, Joost

    2011-12-14

    The ultrafast dynamics of the cationic hole formed in bulk liquid water following ionization is investigated by ab initio molecular dynamics simulations and an experimentally accessible signature is suggested that might be tracked by femtosecond pump-probe spectroscopy. This is one of the fastest fundamental processes occurring in radiation-induced chemistry in aqueous systems and biological tissue. However, unlike the excess electron formed in the same process, the nature and time evolution of the cationic hole has been hitherto little studied. Simulations show that an initially partially delocalized cationic hole localizes within {approx}30 fs after which proton transfer to a neighboring water molecule proceeds practically immediately, leading to the formation of the OH radical and the hydronium cation in a reaction which can be formally written as H{sub 2}O{sup +}+ H{sub 2}O {yields} OH + H{sub 3}O{sup +}. The exact amount of initial spin delocalization is, however, somewhat method dependent, being realistically described by approximate density functional theory methods corrected for the self-interaction error. Localization, and then the evolving separation of spin and charge, changes the electronic structure of the radical center. This is manifested in the spectrum of electronic excitations which is calculated for the ensemble of ab initio molecular dynamics trajectories using a quantum mechanics/molecular mechanics (QM/MM) formalism applying the equation of motion coupled-clusters method to the radical core. A clear spectroscopic signature is predicted by the theoretical model: as the hole transforms into a hydroxyl radical, a transient electronic absorption in the visible shifts to the blue, growing toward the near ultraviolet. Experimental evidence for this primary radiation-induced process is sought using femtosecond photoionization of liquid water excited with two photons at 11 eV. Transient absorption measurements carried out with {approx}40 fs time

  9. Photoionization of chlorine-like potassium and calcium ions

    NASA Astrophysics Data System (ADS)

    Alna'Washi, Ghassan A.

    Absolute photoionization cross-section measurements were performed for a mixture of 2Po 3/2 ground state and 2Po 1/2 metastable state Cl-like K2+ and Ca3+ ions over the photon energy range 44.240-69.741 eV for K2+ and 65.7-104.6 eV for Ca3+. The measurements were performed by merging an ion beam with a beam of synchrotron radiation from an undulator magnet using the ion-photon merged-beams endstation on beamline 10.0.1 of the Advanced Light Source (ALS) at Lawrence Berkley National Laboratory. High resolution measurements were performed near the 2P o 3/2 ground-state ionization threshold for both ions. The ground-state ionization thresholds of K2+ and Ca 3+ was measured to be 45.740 +/- 0.015 eV and 67.070 +/- 0.018 eV, respectively. These energies are respectively 0.066 eV and 0.200 eV lower than the tabulated values in the NIST database. These data are compared to previous measurements for Cl-like Ar+. Most of the observed resonance features belong to multiple Rydberg series of transitions to autoionizing states. These features were assigned spectroscopically using the quantum defect form of the Rydberg formula, guided by calculations of the energies and oscillator strengths of transitions to autoionizing states performed using the pseudo-relativistic Cowan Hartree-Fock atomic structure code. The measurements for Ca3+ compare favorably with recent unpublished R-matrix calculations performed by McLaughlin in a close-coupling expansion within the semi-relativistic Breit-Pauli approximation. This includes the energy positions of the calculated resonances and the magnitudes of the resonant and nonresonant components of the cross section.

  10. Ionization of cytosine monomer and dimer studied by VUV photoionization and electronic structure calculations

    SciTech Connect

    Kostko, Oleg; Bravaya, Ksenia; Krylov, Anna; Ahmed, Musahid

    2009-12-14

    We report a combined theoretical and experimental study of ionization of cytosine monomers and dimers. Gas-phase molecules are generated by thermal vaporization of cytosine followed by expansion of the vapor in a continuous supersonic jet seeded in Ar. The resulting species are investigated by single photon ionization with tunable vacuum-ultraviolet (VUV) synchrotron radiation and mass analyzed using reflectron mass spectrometry. Energy onsets for the measured photoionization efficiency (PIE) spectra are 8.60+-0.05 eV and 7.6+-0.1 eV for the monomer and the dimer, respectively, and provide an estimate for the adiabatic ionization energies (AIE). The first AIE and the ten lowest vertical ionization energies (VIEs) for selected isomers of cytosine dimer computed using equation-of-motion coupled-cluster (EOM-IP-CCSD) method are reported. The comparison of the computed VIEs with the derivative of the PIE spectra, suggests that multiple isomers of the cytosine dimer are present in the molecular beam. The calculations reveal that the large red shift (0.7 eV) of the first IE of the lowest-energy cytosine dimer is due to strong inter-fragment electrostatic interactions, i.e., the hole localized on one of the fragments is stabilized by the dipole moment of the other. A sharp rise in the CH+ signal at 9.20+-0.05 eV is ascribed to the formation of protonated cytosine by dissociation of the ionized dimers. The dominant role of this channel is supported by the computed energy thresholds for the CH+ appearance and the barrierless or nearly barrierless ionization-induced proton transfer observed for five isomers of the dimer.

  11. Real-time monitoring of trace-level VOCs by an ultrasensitive compact lamp-based VUV photoionization mass spectrometer

    NASA Astrophysics Data System (ADS)

    Sun, W. Q.; Shu, J. N.; Zhang, P.; Li, Z.; Li, N. N.; Liang, M.; Yang, B.

    2015-06-01

    In this study, we report on the development of a compact lamp-based vacuum ultraviolet (VUV) photoionization mass spectrometer (PIMS; hereafter referred to as VUV-PIMS) in our laboratory; it is composed of a radio frequency-powered VUV lamp, a VUV photoionizer, an ion-immigration region, and a reflection time-of-flight mass spectrometer. By utilizing the novel photoionizer consisting of a photoionization cavity and a VUV light baffle, extremely low background noise was obtained. An ultrasensitive detection limit (2σ) of 3 pptv was achieved for benzene after an acquisition time of 10 s. To examine its potential for application in real-time sample monitoring, the developed VUV-PIMS was employed for the continuous measurement of urban air for six days in Beijing, China. Strong signals of trace-level volatile organic compounds such as benzene and its alkylated derivatives were observed in the mass spectra. These initial experimental results reveal that the instrument can be used for the online monitoring of trace-level species in the atmosphere.

  12. Absolute Total Photoionization Cross Section of C60 in the Range of 25-120 eV: Revisited

    NASA Astrophysics Data System (ADS)

    Kafle, Bhim P.; Katayanagi, Hideki; Prodhan, Md. Serajul I.; Yagi, Hajime; Huang, Chaoqun; Mitsuke, Koichiro

    2008-01-01

    The absolute total photoionization cross section σabs,I of gaseous C60 is measured in the photon energy hν range from 25 to 120 eV by photoionization mass spectrometry with synchrotron radiation. The absolute detection efficiencies of photoions in different charge states are evaluated. The present σabs,I curve is combined with the photoabsorption cross section curves of C60 at hν=3.5--26 eV in the literature, after appropriate alterations of the vapor pressure are taken into account. The oscillator strengths are computed from the composite curve to be 178.5 and 230.5 for the hν ranges from 3.5 to 40.8 eV and from 3.5 to 119 eV, respectively. These oscillator strengths agree well with those expected from the Thomas-Kuhn-Reiche sum rule and 60 times the photoabsorption cross section of a carbon atom. Moreover, the present σabs,I curve behaves similarly to the relative photoionization cross section curve reported by Reinköster et al.

  13. IPOPv2: Photoionization of Ni XIV - a test case

    NASA Astrophysics Data System (ADS)

    Delahaye, F.; Palmeri, P.; Quinet, P.; Zeippen, C. J.

    2013-12-01

    Several years ago, M. Asplund and coauthors (2004) proposed a revision of the Solar composition. The use of this new prescription for Solar abundances in standard stellar models generated a strong disagreement between the predictions and the observations of Solar observables. Many claimed that the Standard Solar Model (SSM) was faulty, and more specifically the opacities used in such models. As a result, activities around the stellar opacities were boosted. New experiments (J. Bailey at Sandia on Z-Pinch, The OPAC consortium at LULI200) to measure directly absorbtion coefficients have been realized or are underway. Several theoretical groups (CEA-OPAS, Los Alamos Nat. Lab., CEA-SCORCG, The Opacity Project - The Iron Project (IPOPv2)) have started new sets of calculations using different approaches and codes. While the new results seem to confirm the good quality of the opacities used in SSM, it remains important to improve and complement the data currently available. We present recent results in the case of the photoionization cross sections for Ni XIV (Ni13+) from IPOPv2 and possible implications on stellar modelling.

  14. Microfabricated planar glass gas chromatography with photoionization detection.

    PubMed

    Lewis, Alastair C; Hamilton, Jacqueline F; Rhodes, Christopher N; Halliday, Jaydene; Bartle, Keith D; Homewood, Philip; Grenfell, Robin J P; Goody, Brian; Harling, Alice M; Brewer, Paul; Vargha, Gergely; Milton, Martin J T

    2010-01-29

    We report the development of a microfabricated gas chromatography system suitable for the separation of volatile organic compounds (VOCs) and compatible with use as a portable measurement device. Hydrofluoric acid etching of 95x95mm Schott B270 wafers has been used to give symmetrical hemi-spherical channels within a glass substrate. Two matching glass plates were subsequently cold bonded with the channels aligned; the flatness of the glass surfaces resulted in strong bonding through van der Waals forces. The device comprised gas fluidic interconnections, injection zone and 7.5 and 1.4m long, 320microm internal diameter capillaries. Optical microscopy confirmed the capillaries to have fully circular channel profiles. Direct column heating and cooling could be achieved using a combination of resistive heaters and Peltier devices. The low thermal conductivity of glass allowed for multiple uniform temperature zones to be achieved within a single glass chip. Temperature control over the range 10-200 degrees C was achieved with peak power demand of approximately 25W. The 7.5m capillary column was static coated with a 2microm film of non-polar dimethylpolysiloxane stationary phase. A standard FID and a modified lightweight 100mW photoionization detector (PID) were coupled to the column and performance tested with gas mixtures of monoaromatic and monoterpene species at the parts per million concentration level. The low power GC-PID device showed good performance for a small set of VOCs and sub ng detection sensitivity to monoaromatics.

  15. Global nonresonant vibrational-photoelectron coupling in molecular photoionization

    NASA Astrophysics Data System (ADS)

    Poliakoff, Erwin; Das, Aloke; Hardy, David; Bozek, John; Aguilar, Alex; Lucchese, Robert

    2009-05-01

    Using photoelectron spectroscopy and Schwinger variational scattering theory, we have investigated the coupling between vibrational motion and the exiting photoelectron over extended ranges of photoelectron kinetic energy. Photoelectron spectroscopy is performed with vibrational resolution over uncommonly large ranges of energy (ca. 200 eV). We find clear and significant changes in vibrational branching ratios as a function of photon energy, in direct contradiction to predictions of the Franck-Condon principle. While it is well known that resonances lead to coupling between electronic and vibrational degrees of freedom, nonresonant mechanisms that result in such coupling are not expected or well-documented. Photoelectron spectra are presented for several electronic states of N2^+, CO^+, and NO^+, and we find that valence isoelectronic channels behave very differently, which is also surprising. Theoretical results indicate that Cooper minima are the underlying cause of these effects, and we are currently working to understand the reasons for the sensitivity of the Cooper minima on bond length.

  16. Galaxy formation with local photoionization feedback - I. Methods

    NASA Astrophysics Data System (ADS)

    Kannan, R.; Stinson, G. S.; Macciò, A. V.; Hennawi, J. F.; Woods, R.; Wadsley, J.; Shen, S.; Robitaille, T.; Cantalupo, S.; Quinn, T. R.; Christensen, C.

    2014-01-01

    We present a first study of the effect of local photoionizing radiation on gas cooling in smoothed particle hydrodynamics simulations of galaxy formation. We explore the combined effect of ionizing radiation from young and old stellar populations. The method computes the effect of multiple radiative sources using the same tree algorithm as used for gravity, so it is computationally efficient and well resolved. The method foregoes calculating absorption and scattering in favour of a constant escape fraction for young stars to keep the calculation efficient enough to simulate the entire evolution of a galaxy in a cosmological context to the present day. This allows us to quantify the effect of the local photoionization feedback through the whole history of a galaxy's formation. The simulation of a Milky Way-like galaxy using the local photoionization model forms ˜40 per cent less stars than a simulation that only includes a standard uniform background UV field. The local photoionization model decreases star formation by increasing the cooling time of the gas in the halo and increasing the equilibrium temperature of dense gas in the disc. Coupling the local radiation field to gas cooling from the halo provides a preventive feedback mechanism which keeps the central disc light and produces slowly rising rotation curves without resorting to extreme feedback mechanisms. These preliminary results indicate that the effect of local photoionizing sources is significant and should not be ignored in models of galaxy formation.

  17. E × B probe measurements in molecular and electronegative plasmas.

    PubMed

    Renaud, D; Gerst, D; Mazouffre, S; Aanesland, A

    2015-12-01

    This paper reports on the design, the building, the calibration, and the use of a compact E × B probe that acts as a velocity filter or a mass filter for ion species. A series of measurements has been performed in the discharge and in the beam of the PEGASES (Plasma Propulsion with Electronegative GASES) ion source. PEGASES is a unique inductively coupled radio-frequency source able to generate a beam of positive and negative ions when operated with an electronegative gas. In this study, experiments have been carried out with SF6. Calibrated E × B probe spectra indicate that the diagnostic tool can be used to determine the ion velocity and the plasma composition even when many molecular fragments are present. In addition, the probe is able to detect both positive and negative ions. Measurements show a large variety of positively charged ions coming from SF6. Conversely, the beam is solely composed of F(-) and SF6(-) negative ions in compliance with computer simulations.

  18. Molecular Oxygen in the Thermosphere: Issues and Measurement Strategies

    NASA Astrophysics Data System (ADS)

    Picone, J. M.; Hedin, A. E.; Drob, D. P.; Meier, R. R.; Bishop, J.; Budzien, S. A.

    2002-05-01

    We review the state of empirical knowledge regarding the distribution of molecular oxygen in the lower thermosphere (100-200 km), as embodied by the new NRLMSISE-00 empirical atmospheric model, its predecessors, and the underlying databases. For altitudes above 120 km, the two major classes of data (mass spectrometer and solar ultraviolet [UV] absorption) disagree significantly regarding the magnitude of the O2 density and the dependence on solar activity. As a result, the addition of the Solar Maximum Mission (SMM) data set (based on solar UV absorption) to the NRLMSIS database has directly impacted the new model, increasing the complexity of the model's formulation and generally reducing the thermospheric O2 density relative to MSISE-90. Beyond interest in the thermosphere itself, this issue materially affects detailed models of ionospheric chemistry and dynamics as well as modeling of the upper atmospheric airglow. Because these are key elements of both experimental and operational systems which measure and forecast the near-Earth space environment, we present strategies for augmenting the database through analysis of existing data and through future measurements in order to resolve this issue.

  19. E × B probe measurements in molecular and electronegative plasmas

    NASA Astrophysics Data System (ADS)

    Renaud, D.; Gerst, D.; Mazouffre, S.; Aanesland, A.

    2015-12-01

    This paper reports on the design, the building, the calibration, and the use of a compact E × B probe that acts as a velocity filter or a mass filter for ion species. A series of measurements has been performed in the discharge and in the beam of the PEGASES (Plasma Propulsion with Electronegative GASES) ion source. PEGASES is a unique inductively coupled radio-frequency source able to generate a beam of positive and negative ions when operated with an electronegative gas. In this study, experiments have been carried out with SF6. Calibrated E × B probe spectra indicate that the diagnostic tool can be used to determine the ion velocity and the plasma composition even when many molecular fragments are present. In addition, the probe is able to detect both positive and negative ions. Measurements show a large variety of positively charged ions coming from SF6. Conversely, the beam is solely composed of F- and SF 6- negative ions in compliance with computer simulations.

  20. L -shell photoionization of M n5 + to M n8 + ions

    NASA Astrophysics Data System (ADS)

    Blancard, C.; Cubaynes, D.; Guilbaud, S.; Bizau, J.-M.

    2017-07-01

    Resonant photoionization cross sections of M nn + (n =5 to 8) ions are measured in absolute values in the photon energy range of the 2 p →3 d transitions (645 -690 eV ) using a merged-beams setup at the SOLEIL synchrotron radiation facility. The experimental cross sections are compared to calculations we performed using a multiconfiguration Dirac-Fock code and the opas code dedicated to radiative opacity calculations of hot and dense plasmas. Both calculations reproduce the measurements well.

  1. Triggering Excimer Lasers by Photoionization from Corona Discharges

    NASA Astrophysics Data System (ADS)

    Xiong, Zhongmin; Duffey, Thomas; Brown, Daniel; Kushner, Mark

    2009-10-01

    High repetition rate ArF (192 nm) excimer lasers are used for photolithography sources in microelectronics fabrication. In highly attaching gas mixtures, preionization is critical to obtaining stable, reproducible glow discharges. Photoionization from a separate corona discharge is one technique for preionization which triggers the subsequent electron avalanche between the main electrodes. Photoionization triggering of an ArF excimer laser sustained in multi-atmosphere Ne/Ar/F2/Xe gas mixtures has been investigated using a 2-dimensional plasma hydrodynamics model including radiation transport. Continuity equations for charged and neutral species, and Poisson's equation are solved coincident with the electron temperature with transport coefficients obtained from solutions of Boltzmann's equation. Photoionizing radiation is produced by a surface discharge which propagates along a corona-bar located adjacent to the discharge electrodes. The consequences of pulse power waveform, corona bar location, capacitance and gas mixture on uniformity, symmetry and gain of the avalanche discharge will be discussed.

  2. Design of Laboratory Experiments to Study Photoionization Fronts

    NASA Astrophysics Data System (ADS)

    Gray, William James; Davis, Josh; Drake, R. Paul

    2017-06-01

    Here we present the theoretical foundation for a laboratory experiment to study photoionization fronts. Photoionization fronts play important roles in the formation and evolution of structure in the Universe. A properly designed experiment will have to control the recombination rate, electron impact ionization rate, and the initial thermal spectrum. We show that such an experiment can be designed, but requires the use of the largest high-energy-density laser facilities, such as Omega, Z, and NIF. We also show that prior experiments do not actually generate photoionization fronts, rather a heat front is produced by heat conductions. We show some initial simulation results of the current experimental design and characterize the ionization front.

  3. Depth-resolved subcycle dynamics of photoionization in solids

    NASA Astrophysics Data System (ADS)

    Zhokhov, P. A.; Zheltikov, A. M.

    2017-09-01

    We develop a theoretical framework for the analysis of ultrafast dynamics of photoionization in solids that treats the electron density buildup resolved within the field cycle jointly with the propagation dynamics of the laser driver. We show that while the standard, cycle-averaging photoionization models predict a monotonic buildup of the electron density within the driver pulse, the cycle-resolved photoionization model used in this work reveals a subcycle modulation of optical properties of a solid, giving rise to complex patterns of reflected and transmitted fields and providing a source for optical harmonic generation. Propagation effects are shown to heavily distort the spectra of high-order harmonics. Still, the analysis of harmonic spectra and the temporal structure of the harmonic field reveals physically significant properties of the nonlinear-optical response, suggesting the existence of attosecond bursts of interband optical-harmonic emission.

  4. Dynamics of photoionization of hydrogenlike ions in Debye plasmas

    SciTech Connect

    Qi, Y. Y.; Wang, J. G.; Janev, R. K.

    2009-12-15

    Photoionization processes for the ground state and n<=3 excited states of hydrogenlike ions embedded in a weakly coupled plasma are investigated in the entire energy range of a nonrelativistic regime. The plasma screening of the Coulomb interaction between charged particles is described by the Debye-Hueckel model. The energy levels and wave functions for both the bound and continuum states are calculated by solving the Schroedinger equation numerically by the symplectic integrator. The screening of Coulomb interactions reduces the number of bound electron states, decreases their binding energies, broadens the radial distribution of electron wave functions of these states, and changes significantly the phases and the amplitudes of continuum wave functions. These changes strongly affect the dipole matrix elements between the bound and continuum states and, hence, the photoionization cross sections. The most significant effects of the screened Coulomb interactions on the energy behavior of photoionization cross sections are manifested in its low-energy behavior (Wigner threshold law), the appearance of multiple shape and virtual-state resonances when the energy levels of upper bound states enter the continuum after certain critical strength of the screening, and in the (slight) reduction of the cross section at high photon energies. All these features of the photoionization cross section are related to the short-range character of the Debye-Hueckel potential. The effects of the potential screening on the Combet-Farnoux and Cooper minima in the photoionization cross section are also investigated. Comparison of calculated photoionization cross sections with the results of other authors, when available, is made.

  5. Atomic Data for Neutron-capture Elements I. Photoionization and Recombination Properties of Low-charge Selenium Ions

    NASA Technical Reports Server (NTRS)

    Sterling, N. C.; Witthoeft, Michael

    2011-01-01

    We present multi-configuration Breit-Pauli AUTOSTRUCTURE calculations of distorted-wave photoionization (PI) cross sections. and total and partial final-state resolved radiative recombination (RR) and dielectronic recombination (DR) rate coefficients for the first six ions of the trans-iron element Se. These calculations were motivated by the recent detection of Se emission lines in a large number of planetary nebulae. Se is a potentially useful tracer of neutron-capture nucleosynthesis. but accurate determinations of its abundance in photoionized nebulae have been hindered by the lack of atomic data governing its ionization balance. Our calculations were carried out in intermediate coupling with semi re1ativistic radial wavefunctions. PI and recombination data were determined for levels within the ground configuration of each ion, and experimental PI cross-section measurements were used to benchmark our results. For DR, we allowed (Delta)n = 0 core excitations, which are important at photoionized plasma temperatures. We find that DR is the dominant recombination process for each of these Se ions at temperatures representative of photoionized nebulae (approx.10(exp 4) K). In order to estimate the uncertainties of these data, we compared results from three different configuration-interaction expansions for each ion, and also tested the sensitivity of the results to the radial scaling factors in the structure calculations. We find that the internal uncertainties are typically 30-50% for the direct PI cross sections and approx.10% for the computed RR rate coefficients, while those for low-temperature DR can be considerably larger (from 15-30% up to two orders of magnitude) due to the unknown energies of near-threshold autoionization resonances. These data are available at the CDS, and fitting coefficients to the total RR and DR rate coefficients are presented. The results are suitable for incorporation into photoionization codes used to numerically simulate

  6. Two-electron photoionization of ground-state lithium

    SciTech Connect

    Kheifets, A. S.; Fursa, D. V.; Bray, I.

    2009-12-15

    We apply the convergent close-coupling (CCC) formalism to single-photon two-electron ionization of the lithium atom in its ground state. We treat this reaction as single-electron photon absorption followed by inelastic scattering of the photoelectron on a heliumlike Li{sup +} ion. The latter scattering process can be described accurately within the CCC formalism. We obtain integrated cross sections of single photoionization leading to the ground and various excited states of the Li{sup +} ion as well as double photoionization extending continuously from the threshold to the asymptotic limit of infinite photon energy. Comparison with available experimental and theoretical data validates the CCC model.

  7. Relativistic theory of the double photoionization of heliumlike atoms

    SciTech Connect

    Yerokhin, Vladimir A.; Surzhykov, Andrey

    2011-09-15

    A fully relativistic calculation of the double photoionization of heliumlike atoms is presented. The approach is based on the partial-wave representation of the Dirac continuum states and accounts for the retardation in the electron-electron interaction as well as the higher-order multipoles of the absorbed photon. The electron-electron interaction is taken into account to the leading order of the perturbation theory. The relativistic effects are shown to become prominent already for the medium-Z ions, changing the shape and the asymptotic behavior of the photon energy dependence of the ratio of the double-to-single photoionization cross section.

  8. Photoionization spectrum of the B2A' state of HCO

    NASA Astrophysics Data System (ADS)

    Foltynowicz, Robert J.; Rupp, Wolfgang; Hedderich, Hartmut G.; Grant, Edward R.

    1999-12-01

    Formyl radicals, excited to specific rovibrational levels of the strongly bent B2A' state are photoionized to form vibrationally excited states of the linear cation by the absorption of a tunable pulse of ultraviolet light from a second laser. Strong and essentially continuous photoionization spectra, which appear at intervals lying 7000 and 12 000 cm -1 above the adiabatic threshold, establish that formyl radicals can be efficiently ionized with a large geometry change at both energies. Non-Franck-Condon intensities suggest multiquantum pathways for vibrational autoionization.

  9. Double K-shell photoionization and universal scaling laws

    NASA Astrophysics Data System (ADS)

    Hoszowska, J.; Kheifets, A. K.; Dousse, J.-Cl; Berset, M.; Bray, I.; Cao, W.; Fennane, K.; Kayser, Y.; Kavčič, M.; Szlachetko, J.; Szlachetko, M.

    2009-11-01

    The photon energy dependence of the double K-shell ionization cross sections for light atoms and He-like ions is reported. The K-shell double photoionization DPI cross-sections for hollow atom production are compared to those of the corresponding He-like counterparts. The relative contribution of the initial-state correlations and final-state electron-electron interactions to the K-shell DPI is addressed. A semiempirical universal scaling of the double photoionization cross sections with the effective nuclear charge for neutral atoms in the range 2 <= Z <= 47 is established.

  10. Absolute Photoionization Cross Sections of Two Cyclic Ketones: Cyclopentanone & Cyclohexanone.

    PubMed

    Price, Chelsea; Fathi, Yasmin; Meloni, Giovanni

    2017-02-23

    Absolute photoionization cross sections for cyclopentanone and cyclohexanone, as well as partial ionization cross sections for the dissociative ionized fragments, are presented in this investigation. Experiments are performed via a multiplexed photoionization mass spectrometer utilizing VUV synchrotron radiation supplied by the Advanced Light Source of Lawrence Berkeley National Laboratory. These results allow the quantification of these species that is relevant to investigate the kinetics and combustion reactions of potential biofuels. The CBS-QB3 calculated values for the adiabatic ionization energies agree well with the experimental values and the identification of possible dissociative fragments is discussed for both systems.

  11. Atmospheric pressure photoionization using tunable VUV synchrotron radiation

    NASA Astrophysics Data System (ADS)

    Giuliani, A.; Giorgetta, J.-L.; Ricaud, J.-P.; Jamme, F.; Rouam, V.; Wien, F.; Laprévote, O.; Réfrégiers, M.

    2012-05-01

    We report here the first coupling of an atmospheric pressure photoionization (APPI) source with a synchrotron radiation beamline in the vacuum ultra-violet (VUV). A commercial APPI source of a QStar Pulsar i from AB Sciex was modified to receive photons from the DISCO beamline at the SOLEIL synchrotron radiation facility. Photons are delivered at atmospheric pressure in the 4-20 eV range. The advantages of this new set up, termed SR-APPI, over classical APPI are spectral purity and continuous tunability. The technique may also be used to perform tunable photoionization mass spectrometry on fragile compounds difficult to vaporize by classical methods.

  12. Total photoionization cross-sections of excited electronic states by the algebraic diagrammatic construction-Stieltjes-Lanczos method

    NASA Astrophysics Data System (ADS)

    Ruberti, M.; Yun, R.; Gokhberg, K.; Kopelke, S.; Cederbaum, L. S.; Tarantelli, F.; Averbukh, V.

    2014-05-01

    Here, we extend the L2 ab initio method for molecular photoionization cross-sections introduced in Gokhberg et al. [J. Chem. Phys. 130, 064104 (2009)] and benchmarked in Ruberti et al. [J. Chem. Phys. 139, 144107 (2013)] to the calculation of total photoionization cross-sections of molecules in electronically excited states. The method is based on the ab initio description of molecular electronic states within the many-electron Green's function approach, known as algebraic diagrammatic construction (ADC), and on the application of Stieltjes-Chebyshev moment theory to Lanczos pseudospectra of the ADC electronic Hamiltonian. The intermediate state representation of the dipole operator in the ADC basis is used to compute the transition moments between the excited states of the molecule. We compare the results obtained using different levels of the many-body theory, i.e., ADC(1), ADC(2), and ADC(2)x for the first two excited states of CO, N2, and H2O both at the ground state and the excited state equilibrium or saddle point geometries. We find that the single excitation ADC(1) method is not adequate even at the qualitative level and that the inclusion of double electronic excitations for description of excited state photoionization is essential. Moreover, we show that the use of the extended ADC(2)x method leads to a substantial systematic difference from the strictly second-order ADC(2). Our calculations demonstrate that a theoretical modelling of photoionization of excited states requires an intrinsically double excitation theory with respect to the ground state and cannot be achieved by the standard single excitation methods with the ground state as a reference.

  13. Total photoionization cross-sections of excited electronic states by the algebraic diagrammatic construction-Stieltjes-Lanczos method.

    PubMed

    Ruberti, M; Yun, R; Gokhberg, K; Kopelke, S; Cederbaum, L S; Tarantelli, F; Averbukh, V

    2014-05-14

    Here, we extend the L2 ab initio method for molecular photoionization cross-sections introduced in Gokhberg et al. [J. Chem. Phys. 130, 064104 (2009)] and benchmarked in Ruberti et al. [J. Chem. Phys. 139, 144107 (2013)] to the calculation of total photoionization cross-sections of molecules in electronically excited states. The method is based on the ab initio description of molecular electronic states within the many-electron Green's function approach, known as algebraic diagrammatic construction (ADC), and on the application of Stieltjes-Chebyshev moment theory to Lanczos pseudospectra of the ADC electronic Hamiltonian. The intermediate state representation of the dipole operator in the ADC basis is used to compute the transition moments between the excited states of the molecule. We compare the results obtained using different levels of the many-body theory, i.e., ADC(1), ADC(2), and ADC(2)x for the first two excited states of CO, N2, and H2O both at the ground state and the excited state equilibrium or saddle point geometries. We find that the single excitation ADC(1) method is not adequate even at the qualitative level and that the inclusion of double electronic excitations for description of excited state photoionization is essential. Moreover, we show that the use of the extended ADC(2)x method leads to a substantial systematic difference from the strictly second-order ADC(2). Our calculations demonstrate that a theoretical modelling of photoionization of excited states requires an intrinsically double excitation theory with respect to the ground state and cannot be achieved by the standard single excitation methods with the ground state as a reference.

  14. Online study on the co-pyrolysis of coal and corn with vacuum ultraviolet photoionization mass spectrometry.

    PubMed

    Weng, Jun-Jie; Liu, Yue-Xi; Zhu, Ya-Nan; Pan, Yang; Tian, Zhen-Yu

    2017-11-01

    With the aim to support the experimental tests in a circulating fluidized bed pilot plant, the pyrolysis processes of coal, corn, and coal-corn blend have been studied with an online pyrolysis photoionization time-of-flight mass spectrometry (Py-PI-TOFMS). The mass spectra at different temperatures (300-800°C) as well as time-evolved profiles of selected species were measured. The pyrolysis products such as alkanes, alkenes, phenols, aromatics, as well as nitrogen- and sulfur-containing species were detected. As temperature rises, the relative ion intensities of high molecular weight products tend to decrease, while those of aromatics increase significantly. During the co-pyrolysis, coal can promote the reaction temperature of cellulose in corn. Time-evolved profiles demonstrate that coal can affect pyrolysis rate of cellulose, hemicellulose, and lignin of corn in blend. This work shows that Py-PI-TOFMS is a powerful approach to permit a better understanding of the mechanisms underlying the co-pyrolysis of coal and biomass. Copyright © 2017 Elsevier Ltd. All rights reserved.

  15. Measuring the Kinetics of Molecular Association by Isothermal Titration Calorimetry.

    PubMed

    Vander Meulen, Kirk A; Horowitz, Scott; Trievel, Raymond C; Butcher, Samuel E

    2016-01-01

    The real-time power response inherent in an isothermal titration calorimetry (ITC) experiment provides an opportunity to directly analyze association kinetics, which, together with the conventional measurement of thermodynamic quantities, can provide an incredibly rich description of molecular binding in a single experiment. Here, we detail our application of this method, in which interactions occurring with relaxation times ranging from slightly below the instrument response time constant (12.5 s in this case) to as large as 600 s can be fully detailed in terms of both the thermodynamics and kinetics. In a binding titration scenario, in the most general case an injection can reveal an association rate constant (kon). Under more restrictive conditions, the instrument time constant-corrected power decay following each injection is simply an exponential decay described by a composite rate constant (kobs), from which both kon and the dissociation rate constant (koff) can be extracted. The data also support the viability of this exponential approach, for kon only, for a slightly larger set of conditions. Using a bimolecular RNA folding model and a protein-ligand interaction, we demonstrate and have internally validated this approach to experiment design, data processing, and error analysis. An updated guide to thermodynamic and kinetic regimes accessible by ITC is provided.

  16. Ultrafast Dynamics in Postcollision Interaction after Multiple Auger Decays in Argon 1s Photoionization

    NASA Astrophysics Data System (ADS)

    Guillemin, R.; Sheinerman, S.; Bomme, C.; Journel, L.; Marin, T.; Marchenko, T.; Kushawaha, R. K.; Trcera, N.; Piancastelli, M. N.; Simon, M.

    2012-07-01

    Argon 1s photoionization followed by multiple Auger decays is investigated both experimentally, by means of photoelectron-ion coincidences, and theoretically. A strong influence of the different Auger decays on the photoelectron spectra is observed through postcollision interaction which shifts the maximum of the energy distribution and distorts the spectral shape. A good agreement between the calculated and measured spectra for selected Arn+ ions (n=1-5) allows one to estimate the widths (lifetimes) of the intermediate states for each specific decay pathway.

  17. Kinetic energies of fragment ions produced by dissociative photoionization of NO

    NASA Technical Reports Server (NTRS)

    Samson, J. A. R.; Angel, G. C.; Rstgi, O. P.

    1985-01-01

    The kinetic energies of ions produced by dissociative photoionization of NO have been measured at the discrete resonance lines of He (584A) and Ne (736A), and with undispersed synchrotron radiation. O sup + ions were identified with energies from 0 to approximately 0.5 eV and two groups of N sup + ions one with energy of 0.36 eV and another with energies between 0.9 and 1.5 eV, apparently produced by predissociation of the C sup 3 P 1 and B'1 sigma states respectively.

  18. Confinement Resonances in Photoionization of Xe-C{sub 60}{sup +}

    SciTech Connect

    Kilcoyne, A. L. D.; Aguilar, A.; Mueller, A.; Schippers, S.; Cisneros, C.; Alna'Washi, G.; Aryal, N. B.; Baral, K. K.; Esteves, D. A.; Thomas, C. M.; Phaneuf, R. A.

    2010-11-19

    Experimental evidence is presented for confinement resonances associated with photoabsorption by a Xe atom in a C{sub 60} cage. The giant 4d resonance in photoionization of Xe is predicted to be redistributed into four components due to multipath interference of photoelectron waves reflected by the cage. The measurements were made in the photon energy range 60-150 eV by merging a beam of synchrotron radiation with a mass/charge selected Xe-C{sub 60}{sup +} ion beam. The phenomenon was observed in the Xe-C{sub 583}{sup +} product ion channel.

  19. Resonant and Near-Threshold Photoionization Cross Sections of Fe{sup 14+}

    SciTech Connect

    Simon, M. C.; Crespo Lopez-Urrutia, J. R.; Beilmann, C.; Schwarz, M.; Epp, S. W.; Schmitt, B. L.; Baumann, T. M.; Bernitt, S.; Ginzel, R.; Keitel, C. H.; Klawitter, R.; Kubicek, K.; Maeckel, V.; Mokler, P. H.; Ullrich, J.; Harman, Z.; Behar, E.; Follath, R.; Reichardt, G.; Schwarzkopf, O.

    2010-10-29

    Photoionization (PI) of Fe{sup 14+} in the range from 450 to 1100 eV was measured at the BESSY II storage ring using an electron beam ion trap achieving high target-ion area densities of 10{sup 10} cm{sup -2}. Photoabsorption by this ion is observed in astrophysical spectra and plasmas, but until now cross sections and resonance energies could only be provided by calculations. We reach a resolving power E/{Delta}E of at least 6500, outstanding in the present energy range, which enables benchmarking and improving the most advanced theories for PI of ions in high charge states.

  20. Vibrationally resolved 2a 2u-1 photoionization of C 6F 6

    NASA Astrophysics Data System (ADS)

    Wu, Chuanyong; Poliakoff, E. D.

    1998-07-01

    We report vibrationally resolved results on 2a 2u-1 photoionization of C 6F 6. Vibrational branching ratios are determined for the ring breathing mode by measuring dispersed fluorescence spectra of the C 6F 6+ ( B˜ 2A2 u→ X˜ 2E1 g) transition. Data are presented in the excitation energy range from 20 to 35 eV, and the vibrational branching ratios show a striking departure from Franck-Condon behavior from 20 to 25 eV. This deviation is attributed to a shape resonance.

  1. Total and dissociative photoionization cross sections of N2 from threshold to 107 eV

    NASA Technical Reports Server (NTRS)

    Samson, James A. R.; Masuoka, T.; Pareek, P. N.; Angel, G. C.

    1986-01-01

    The absolute cross sections for the production of N(+) and N2(+) were measured from the dissociative ionization threshold of 115 A. In addition, the absolute photoabsorption and photoionization cross sections were tabulated between 114 and 796 A. The ionization efficiencies were also given at several discrete wave lengths between 660 and 790 A. The production of N(+) fragment ions are discussed in terms of the doubly excited N2(+) states with binding energies in the range of 24 to 44 eV.

  2. Protonation enhancement by dichloromethane doping in low-pressure photoionization

    NASA Astrophysics Data System (ADS)

    Shu, Jinian; Zou, Yao; Xu, Ce; Li, Zhen; Sun, Wanqi; Yang, Bo; Zhang, Haixu; Zhang, Peng; Ma, Pengkun

    2016-12-01

    Doping has been used to enhance the ionization efficiency of analytes in atmospheric pressure photoionization, which is based on charge exchange. Compounds with excellent ionization efficiencies are usually chosen as dopants. In this paper, we report a new phenomenon observed in low-pressure photoionization: Protonation enhancement by dichloromethane (CH2Cl2) doping. CH2Cl2 is not a common dopant due to its high ionization energy (11.33 eV). The low-pressure photoionization source was built using a krypton VUV lamp that emits photons with energies of 10.0 and 10.6 eV and was operated at ~500–1000 Pa. Protonation of water, methanol, ethanol, and acetaldehyde was respectively enhanced by 481.7 ± 122.4, 197.8 ± 18.8, 87.3 ± 7.8, and 93.5 ± 35.5 times after doping 291 ppmv CH2Cl2, meanwhile CH2Cl2 almost does not generate noticeable ions itself. This phenomenon has not been documented in the literature. A new protonation process involving in ion-pair and H-bond formations was proposed to expound the phenomenon. The observed phenomenon opens a new prospect for the improvement of the detection efficiency of VUV photoionization.

  3. Protonation enhancement by dichloromethane doping in low-pressure photoionization

    PubMed Central

    Shu, Jinian; Zou, Yao; Xu, Ce; Li, Zhen; Sun, Wanqi; Yang, Bo; Zhang, Haixu; Zhang, Peng; Ma, Pengkun

    2016-01-01

    Doping has been used to enhance the ionization efficiency of analytes in atmospheric pressure photoionization, which is based on charge exchange. Compounds with excellent ionization efficiencies are usually chosen as dopants. In this paper, we report a new phenomenon observed in low-pressure photoionization: Protonation enhancement by dichloromethane (CH2Cl2) doping. CH2Cl2 is not a common dopant due to its high ionization energy (11.33 eV). The low-pressure photoionization source was built using a krypton VUV lamp that emits photons with energies of 10.0 and 10.6 eV and was operated at ~500–1000 Pa. Protonation of water, methanol, ethanol, and acetaldehyde was respectively enhanced by 481.7 ± 122.4, 197.8 ± 18.8, 87.3 ± 7.8, and 93.5 ± 35.5 times after doping 291 ppmv CH2Cl2, meanwhile CH2Cl2 almost does not generate noticeable ions itself. This phenomenon has not been documented in the literature. A new protonation process involving in ion-pair and H-bond formations was proposed to expound the phenomenon. The observed phenomenon opens a new prospect for the improvement of the detection efficiency of VUV photoionization. PMID:27905552

  4. Helium 23S photoionization up to the N = 5 threshold

    NASA Astrophysics Data System (ADS)

    Argenti, Luca; Moccia, Roberto

    2008-02-01

    We present the results of an accurate B-spline K-matrix calculation of total and partial cross sections and asymmetry parameters for the photoionization of the metastable 23Se state of helium up to the N = 5 threshold. The effect of the [040]+5 intruder state below N = 4 is shown.

  5. Photodissociation of Acetaldehyde and the Photoionization Cross Section of HCO

    NASA Astrophysics Data System (ADS)

    Shubert, V. Alvin; Pratt, Stephen T.

    2010-06-01

    Acetaldehyde was photodissociated with near UV laser light, and the methyl (CH_3) and formyl (HCO) radical fragments were photoionized with vacuum ultraviolet (VUV) light. The fragments were detected by using both time of flight mass spectrometry and velocity ion map imaging. With the former technique, simultaneous detection of both fragments provided the intensity of HCO+ relative to CH_3+ with I(HCO+)/I(CH_3+) ≈ 0.8. Because the absolute photoionization cross section of the CH_3 radical has been characterized (≈ 5 Mb) at the VUV energies of interest, the absolute photoionization cross section of HCO could be determined from the intensity ratio, yielding an HCO cross section of ≈ 4 Mb at 10.3 eV. However, because some of the HCO fragments could be formed with enough internal energy to undergo secondary dissociation, velocity ion map imaging was employed to determine the extent of any secondary dissociation that occurred. The translational energy distributions obtained for both the CH_3 and HCO fragments are nearly identical, indicating that no HCO fragments underwent secondary dissociation. A surprising result was the smaller photoionization cross section of HCO relative to CH_3. Comparison to the isoelectronic species of NO will be discussed and a potential explanation will be offered for this observation. This work was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences under contract No. DE-AC02-06CH11357.

  6. Photoionization of hydrogen-like ions in dense quantum plasmas

    NASA Astrophysics Data System (ADS)

    Qi, Y. Y.; Wang, J. G.; Janev, R. K.

    2017-06-01

    The photoionization of hydrogen-like ions in n ≤ 3 bound states, embedded in cold, dense quantum plasmas, is investigated in detail. The electron energies and wave functions for the bound and continuum states are determined by numerically solving the scaled Schrödinger equation by the fourth-order symplectic integration scheme. The monotonic behavior of the photoionization cross section for a pure Coulomb potential is dramatically changed due to the plasma screening effects described by the cosine-Debye-Hückel potential. In the region of low photoelectron energies, the photoionization cross section, besides the usual Wigner-law threshold behavior, exhibits a rich structure of shape and virtual-state resonances when the plasma screening parameter takes values around the critical screening parameter for which a bound state enters the continuum. It is observed that a shape resonance is followed by a Cooper minimum in the photoionization cross section when the principal quantum number of continuum quasi-bound state is equal to the one of the initial bound states.

  7. Atomic kinetics of a neon photoionized plasma experiment at Z

    NASA Astrophysics Data System (ADS)

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

    2017-06-01

    We discuss an experimental effort to study the atomic kinetics in neon photoionized plasmas via K-shell line absorption spectroscopy. The experiment employs the intense x-ray flux emitted at the collapse of a Z-pinch to heat and backlight a photoionized plasma contained within a cm-scale gas cell placed at various distances from the Z-pinch and filled with neon gas pressures in the range from 3.5 to 30 torr. The experimental platform affords an order of magnitude range in the ionization parameter characterizing the photoionized plasma from about 3 to 80 erg*cm/s. Thus, the experiment allows for the study of trends in ionization distribution as a function of the ionization parameter. An x-ray crystal spectrometer capable of collecting both time-integrated and time-gated spectra is used to collect absorption spectra. A suite of IDL programs has been developed to process the experimental data to produce transmission spectra. The spectra show line absorption by several ionization stages of neon, including Be-, Li-, He-, and H-like ions. Analysis of these spectra yields ion areal-densities and charge state distributions, which can be compared with results from atomic kinetics codes. In addition, the electron temperature is extracted from level population ratios of nearby energy levels in Li- and Be-like ions, which can be used to test heating models of photoionized plasmas.

  8. Dissociative photoionization of ethyl acrylate: Theoretical and experimental insights

    NASA Astrophysics Data System (ADS)

    Song, Yanlin; Chen, Jun; Ding, Mengmeng; Wei, Bin; Cao, Maoqi; Shan, Xiaobin; Zhao, Yujie; Huang, Chaoqun; Sheng, Liusi; Liu, Fuyi

    2015-08-01

    The photoionization and dissociation of ethyl acrylate have been investigated by time-of-flight mass spectrometer with tunable vacuum ultraviolet (VUV) source in the range of 9.0-20.0 eV. The photoionization mass spectrum (PIMS) for ethyl acrylate and photoionization efficiency (PIE) curves for its major fragment ions: C5H7O2+, C4H5O2+, C3H5O2+, C3H4O+, C3H3O+, C2H5O+, C2H3O+, C2H5+ and C2H4+ have been obtained. The formation channels of main fragments are predicted by Gaussian 09 program at G3B3 level and examined via their dissociation energies from experimental results. Based on our analysis, nine main dissociative photoionization channels are proposed: C5H7O2+ + H, C4H5O2+ + CH3, C3H5O2+ + C2H3, C3H4O+ + C2H4O, C3H3O+ + C2H5O, C2H5O+ + C3H3O, C2H3O+ + C3H5O, C2H5+ + C3H3O2, C2H4+ + C3H4O2, respectively. The results of this work lead to a better understanding of photochemistry in the environment.

  9. Electron scattering from and photoionization of open- shell atoms

    NASA Astrophysics Data System (ADS)

    Lin, Dong

    1999-09-01

    The multiconfiguration Hartree-Fock (MCHF) approach, developed by Dr. H. P. Saha et al, has been proved to be extremely successful in the past few years in reproducing experimental results at a very high level of accuracy. The research projects we are interested consist of two areas. In the first area we performed ab initio calculations on elastic scattering of electrons from open-shell sulfur atoms. In the second area, in order to understand the electronic dynamics in photoionization of atoms, we carried out accurate calculations on valence and K-shell photoionization of three-electron systems from lithium through neon for photon energies from threshold to very high energies; to further identify the autoionization resonances which were observed near threshold and to understand the dynamics, we modifies the MCHF method to include relativistic effects and performed calculation on partial photoionization cross section, resonance structure and effect of spin-orbit interaction in photoionization of atomic bromine. The calculated results obtained in each of these investigations are compared with available experimental and theoretical data and are found to be in very good agreement. The research contribution made for the fulfillment of the degree, we understand, will be a valuable addition towards a better understanding of the open-shell systems.

  10. Correlation Effects in the Photoionization of Confined Calcium and Zinc

    NASA Astrophysics Data System (ADS)

    Varma, R. Hari; Manson, S. T.

    2005-05-01

    Studies of atoms confined in an endohedral environment have aroused significant recent interest [1]. In this work, the photoionization @Ca and @Zn have been studied using the Relativistic-Random-Phase Approximation, modified to include the confinement potential. Photoionization of the 4s and 3p subshells of free and confined atomic calcium, along with the 4s, 3d, 3p and 3s subshells of free and confined atomic zinc, have been studied. The photoionization parameters of confined atoms differ significantly from those of their ``free'' counterparts. The dipole cross sections and angular distribution asymmetry parameters exhibit oscillations with energy arising from the back scattering of the escaping electron by the confining potential, i.e., ``confinement resonances'' [2]. These oscillations persist when nondipole matrix elements are also included as is reflected in the nondipole cross section and angular distribution asymmetry parameters [3]; the relative strengths of the oscillations due to back-scattering in the E1 and E2 photoionization parameters have qualitatively different profiles as a function of photon energy. [1] V. K. Dolmatov, A. S. Baltenkov, J.-P. Connerade and S. T. Manson, Radiation Phys. Chem. 70, 417 (2004). [2] M. Ya. Amusia, A. S. Baltenkov, V. K. Dolmatov, S. T. Manson and A. Z. Msezane, Phys. Rev. A 70, 023201 (2004). [3] P.C. Deshmukh, Tanima Banerjee, K. P. Sunanda and R. Hari Varma, Radiation Phys. and Chem (submitted).

  11. Photoionization of Ca XV with high energy features

    NASA Astrophysics Data System (ADS)

    Nahar, Sultana N.

    2017-02-01

    Photoionization cross sections of (Ca XV + hν → Ca XVI + e), with high energy resonant photo-absorption phenomena, of a large number of bound states, 701 in total with n ≤ 10 and l ≤ 9, are reported. They are obtained using the R-matrix method with a close coupling (CC) wavefunction expansion of 29 states of n = 2,3 complexes of the core ion Ca XVI. Characteristic features found in photoionization of the ion are illustrated with examples. The cross section (σPI) of the ground 2s22p2(3P) state is found to be unaffected by the size of the wavefunction expansion except for weak sparse resonances in high energy region. However, effects on excited states are considerable as the core excitations to n = 3 states are manifested in huge resonant absorption in high energy photoionization. They show existence of prominent high peak resonant features and enhancement in the background that were not studied before for Ca XV. In addition photoionization of the excited states with a single valence electron is dominated by Seaton resonant structures formed by the photo-excitation-of-core in the high energy region. These features will impact other quantities, such as the opacity, electron-ion recombination in high temperature plasmas where the ion exists, and hence will play important role in determination of elemental abundances in the astronomical objects.

  12. Protonation enhancement by dichloromethane doping in low-pressure photoionization.

    PubMed

    Shu, Jinian; Zou, Yao; Xu, Ce; Li, Zhen; Sun, Wanqi; Yang, Bo; Zhang, Haixu; Zhang, Peng; Ma, Pengkun

    2016-12-01

    Doping has been used to enhance the ionization efficiency of analytes in atmospheric pressure photoionization, which is based on charge exchange. Compounds with excellent ionization efficiencies are usually chosen as dopants. In this paper, we report a new phenomenon observed in low-pressure photoionization: Protonation enhancement by dichloromethane (CH2Cl2) doping. CH2Cl2 is not a common dopant due to its high ionization energy (11.33 eV). The low-pressure photoionization source was built using a krypton VUV lamp that emits photons with energies of 10.0 and 10.6 eV and was operated at ~500-1000 Pa. Protonation of water, methanol, ethanol, and acetaldehyde was respectively enhanced by 481.7 ± 122.4, 197.8 ± 18.8, 87.3 ± 7.8, and 93.5 ± 35.5 times after doping 291 ppmv CH2Cl2, meanwhile CH2Cl2 almost does not generate noticeable ions itself. This phenomenon has not been documented in the literature. A new protonation process involving in ion-pair and H-bond formations was proposed to expound the phenomenon. The observed phenomenon opens a new prospect for the improvement of the detection efficiency of VUV photoionization.

  13. Electronic decoherence following photoionization: Full quantum-dynamical treatment of the influence of nuclear motion

    NASA Astrophysics Data System (ADS)

    Arnold, Caroline; Vendrell, Oriol; Santra, Robin

    2017-03-01

    Photoionization using attosecond pulses can lead to the formation of coherent superpositions of the electronic states of the parent ion. However, ultrafast electron ejection triggers not only electronic but also nuclear dynamics—leading to electronic decoherence, which is typically neglected on time scales up to tens of femtoseconds. We propose a full quantum-dynamical treatment of nuclear motion in an adiabatic framework, where nuclear wave packets move on adiabatic potential energy surfaces expanded up to second order at the Franck-Condon point. We show that electronic decoherence is caused by the interplay of a large number of nuclear degrees of freedom and by the relative topology of the potential energy surfaces. Application to H2O , paraxylene, and phenylalanine shows that an initially coherent state evolves to an electronically mixed state within just a few femtoseconds. In these examples the fast vibrations involving hydrogen atoms do not affect electronic coherence at short times. Conversely, vibrational modes involving the whole molecular skeleton, which are slow in the ground electronic state, quickly destroy it upon photoionization.

  14. Dissociative photoionization of β-pinene: an experimental and theoretical study.

    PubMed

    Sheng, Liusi; Cao, Maoqi; Chen, Jun; Fang, Wenzhen; Li, Yuquan; Ge, Shaolin; Shan, Xiaobin; Liu, Fuyi; Zhao, Yujie; Zhenya Wang, Zhenya Wang

    2014-01-01

    We investigated the photoionization and dissociation photoionization of the β-pinene molecular using time-of-flight mass spectrometry with a tunable vacuum ultraviolet source in the region from 8.00eV to 15.50eV. The experimental ionization energy (IE) value is 8.60eV using electron impact as the ionization source which is not in good agreement with theoretical value (8.41 eV) with a G3MP2 method. We obtained the accurate IE of β-pinene (8.45 ± 0.03eV) derived from the efficiency spectrum which is in good agreement with the theoretical value (8.38eV) of the CBS-QB3 method. We elucidated the dissociation pathways of primary fragment ions from the β-pinene cation on the basis of experimental observations in combination with theoretical calculations. Most of the dissociation pathways occur via a rearrangement reaction prior to dissociation. We also determined the structures of the transition states and intermediates for those isomerization processes.

  15. Thermal desorption/tunable vacuum-ultraviolet time-of-flight photoionization aerosol mass spectrometry for investigating secondary organic aerosols in chamber experiments.

    PubMed

    Fang, Wenzheng; Gong, Lei; Shan, Xiaobin; Liu, Fuyi; Wang, Zhenya; Sheng, Liusi

    2011-12-01

    This paper describes thermal desorption/tunable vacuum-ultraviolet photoionization time-of-flight aerosol mass spectrometry (TD-VUV-TOF-PIAMS) for the real-time analysis of secondary organic aerosols (SOAs) in smog chamber experiments. SOAs are sampled directly from atmospheric pressure and are focused through an aerodynamic lens assembly into the mass spectrometer. Once the particles have entered the source region, they impact on a heater and are vaporized. The nascent vapor is then softly ionized by tunable VUV synchrotron radiation. TD-VUV-TOF-PIAMS was used in conjunction with the smog chamber to study SOA formation from the photooxidation of toluene with hydroxyl radicals. The ionization energies (IEs) of these SOA products are sometimes very different with each other. As the ideal photon source is tunable, its energy can be adjusted for each molecular to be ionized. The mass spectra obtained at different photon energies are then to be useful for molecular identification. Real-time analysis of the mass spectra of SOAs is compared with previous off-line measurements. These results illustrate the potential of TD-VUV-TOF-PIAMS for direct molecular characterization of SOAs in smog chamber experiments.

  16. Precise Access to the Molecular-Frame Complex Recombination Dipole through High-Harmonic Spectroscopy

    NASA Astrophysics Data System (ADS)

    Schoun, S. B.; Camper, A.; Salières, P.; Lucchese, R. R.; Agostini, P.; DiMauro, L. F.

    2017-01-01

    We report on spectral intensity and group delay measurements of the highest-occupied molecular-orbital (HOMO) recombination dipole moment of N2 in the molecular-frame using high harmonic spectroscopy. We take advantage of the long-wavelength 1.3 μ m driving laser to isolate the HOMO in the near threshold region, 19-67 eV. The precision of our group delay measurements reveals previously unseen angle-resolved spectral features associated with autoionizing resonances, and allows quantitative comparison with cutting-edge correlated 8-channel photoionization dipole moment calculations.

  17. Spin–orbit interaction mediated molecular dissociation

    SciTech Connect

    Kokkonen, E. Jänkälä, K.; Kettunen, J. A.; Heinäsmäki, S.; Karpenko, A.; Huttula, M.; Löytynoja, T.

    2014-05-14

    The effect of the spin–orbit interaction to photofragmentation is investigated in the mercury(II) bromide (HgBr{sub 2}) molecule. Changes in the fragmentation between the two spin–orbit components of Hg 5d photoionization, as well as within the molecular-field-splitted levels of these components are observed. Dissociation subsequent to photoionization is studied with synchrotron radiation and photoelectron-photoion coincidence spectroscopy. The experimental results are accompanied by relativistic ab initio analysis of the photoelectron spectrum.

  18. Rotamers and Migration: Investigating the Dissociative Photoionization of Ethylenediamine.

    PubMed

    Muller, Giel; Voronova, Krisztina; Sztáray, Bálint; Meloni, Giovanni

    2016-06-09

    The unimolecular dissociation of energy-selected ethylenediamine cations was studied by threshold photoelectron photoion coincidence spectroscopy (TPEPICO) in the photon energy range of 8.60-12.50 eV. Modeling the breakdown diagram and time-of-flight distributions with rigid activated complex RRKM theory yielded 0 K appearance energies for eight dissociation channels, leading to NH2CHCH2(+)(•) at 9.120 ± 0.010 eV, CH3C(NH2)2(+) at 9.200 ± 0.012 eV, NH2CHCH3(+) at 9.34 ± 0.08 eV, CH2NH2(+) at 9.449 ± 0.025 eV, CH2NH3(+) at 9.8 ± 0.1 eV, c-C2H4NH2(+) at 10.1 ± 0.1 eV, CH3NHCHCH2(+) at 10.2 ± 0.1 eV, and the reappearance of CH2NH2(+) at 10.2 ± 0.1 eV. The CBS-QB3-calculated pathways highlighted the influence of intramolecular hydrogen attractions on the dissociation processes, presenting novel isomers and low-energy van der Waals intermediates that led to fragments in good agreement with experimental results. While most of the dissociation channels take place through reverse barriers, the 0 K heat of formation of (•)CH2NH2 was determined to be 147.6 ± 3.7 kJ mol(-1), in excellent agreement with literature, and the 0 K heat of formation of CH2NH3(+) at 844 ± 10 kJ mol(-1) is the first experimentally measured value available and is in good agreement with theory.

  19. Photoionization of ground and excited levels of P II

    NASA Astrophysics Data System (ADS)

    Nahar, Sultana N.

    2017-01-01

    Photoionization cross section (σPI) of P II, (hν + P II → P III + e), from ground and a large number of excited levels are presented. The study includes the resonant structures and the characteristics of the background in photoionization cross sections. The present calculations were carried out in the Breit-Pauli R-matrix (BPRM) method that includes relativistic effects. The autoionizing resonances are delineated with a fine energy mesh to observe the fine structure effects. A singular resonance, formed by the coupling of channels in fine structure but not allowed in LS coupling, is seen at the ionization threshold of photoionization for the ground and many excited levels. The background cross section is seen enhanced compared to smooth decay for the excited levels. Examples are presented to illustrate the enhanced background cross sections at the energies of the core levels, 4P3/2 and 2D3/2, that are allowed for electric dipole transitions by the core ground level 2 P1/2o. In addition strong Seaton or photo-excitation-of-core (PEC) resonances are found in the photoionization of single valence electron excited levels. Calculations used a close coupling wave function expansion that included 18 fine structure levels of core P III from configurations 3s23p, 3s3p2, 3s23d, 3s24s, 3s24p and 3p3. Photoionization cross sections are presented for all 475 fine structure levels of P II found with n ≤ 10 and l ≤ 9. The present results will provide high precision parameters of various applications involving this less studied ion.

  20. Photoionization thresholds of rare-earth impurity ions. EuS :CaF2, CeT :YAG, and SmS :CaF2

    SciTech Connect

    Pedrini, C.; Rogemond, F.; McClure, D.S.

    1986-02-15

    The spectral dependence of the photoionization energy of EuS :CaF2, CeT :YAG, and SmS :CaF2 systems have been measured and thresholds experimentally determined and compared with theoretical values calculated from electrostatic models. It is shown that the excited state absorption transitions or the persistent hole burning observed by other authors occur above the threshold energy of photoionization of the impurities and that the states of the crystal which form the bottom of the conduction band may play an important role in the strong probability of these processes. A review of thresholds now known is also given.

  1. Molecular Diode Studies Based on a Highly Sensitive Molecular Measurement Technique

    PubMed Central

    Iwane, Madoka; Fujii, Shintaro; Kiguchi, Manabu

    2017-01-01

    In 1974, molecular electronics pioneers Mark Ratner and Arieh Aviram predicted that a single molecule could act as a diode, in which electronic current can be rectified. The electronic rectification property of the diode is one of basic functions of electronic components and since then, the molecular diode has been investigated as a first single-molecule device that would have a practical application. In this review, we first describe the experimental fabrication and electronic characterization techniques of molecular diodes consisting of a small number of molecules or a single molecule. Then, two main mechanisms of the rectification property of the molecular diode are discussed. Finally, representative results for the molecular diode are reviewed and a brief outlook on crucial issues that need to be addressed in future research is discussed. PMID:28445393

  2. Molecular Diode Studies Based on a Highly Sensitive Molecular Measurement Technique.

    PubMed

    Iwane, Madoka; Fujii, Shintaro; Kiguchi, Manabu

    2017-04-26

    In 1974, molecular electronics pioneers Mark Ratner and Arieh Aviram predicted that a single molecule could act as a diode, in which electronic current can be rectified. The electronic rectification property of the diode is one of basic functions of electronic components and since then, the molecular diode has been investigated as a first single-molecule device that would have a practical application. In this review, we first describe the experimental fabrication and electronic characterization techniques of molecular diodes consisting of a small number of molecules or a single molecule. Then, two main mechanisms of the rectification property of the molecular diode are discussed. Finally, representative results for the molecular diode are reviewed and a brief outlook on crucial issues that need to be addressed in future research is discussed.

  3. Rovibronically selected and resolved two-color laser photoionization and photoelectron study of nickel carbide cation.

    PubMed

    Chang, Yih Chung; Shi, Xiaoyu; Lau, Kai-Chung; Yin, Qing-Zhu; Liou, H T; Ng, C Y

    2010-08-07

    We have performed a two-color laser photoionization and photoelectron study of nickel carbide (NiC) and its cation (NiC(+)). By preparing NiC in a single rovibronic level of an intermediate vibronic state via visible laser excitation prior to ultraviolet laser photoionization, we have measured the photoionization efficiency spectrum of NiC near its ionization threshold, covering the formation of NiC(+)(X (2)Sigma(+);v(+)=0-3). We have also obtained well-resolved rotational transitions for the v(+)=0 and 1 vibrational bands of the NiC(+)(X (2)Sigma(+)) ground state. The assignment of rotational transitions observed between the neutral NiC intermediate state and the NiC(+) ion ground state has allowed the direct determination of a highly precise value for the ionization energy of NiC, IE(NiC)=67,525.1+/-0.5 cm(-1) (8.372 05+/-0.000 06 eV). This experiment also provides reliable values for the vibrational spacing [DeltaG(1/2)=859.5+/-0.5 cm(-1)], rotational constants (B(e)(+)=0.6395+/-0.0018 cm(-1) and alpha(e)(+)=0.0097+/-0.0009 cm(-1)), and equilibrium bond distance (r(e)(+)=1.628 A) for the NiC(+)(X (2)Sigma(+)) ground state. The experimental results presented here are valuable for benchmarking the development of more reliable ab initio quantum computation procedures for energetic and spectroscopic calculations of transition metal-containing molecules.

  4. Rovibronically selected and resolved two-color laser photoionization and photoelectron study of nickel carbide cation

    NASA Astrophysics Data System (ADS)

    Chang, Yih Chung; Shi, Xiaoyu; Lau, Kai-Chung; Yin, Qing-Zhu; Liou, H. T.; Ng, C. Y.

    2010-08-01

    We have performed a two-color laser photoionization and photoelectron study of nickel carbide (NiC) and its cation (NiC+). By preparing NiC in a single rovibronic level of an intermediate vibronic state via visible laser excitation prior to ultraviolet laser photoionization, we have measured the photoionization efficiency spectrum of NiC near its ionization threshold, covering the formation of NiC+(X Σ2+;v+=0-3). We have also obtained well-resolved rotational transitions for the v+=0 and 1 vibrational bands of the NiC+(X Σ2+) ground state. The assignment of rotational transitions observed between the neutral NiC intermediate state and the NiC+ ion ground state has allowed the direct determination of a highly precise value for the ionization energy of NiC, IE(NiC)=67 525.1±0.5 cm-1 (8.372 05±0.000 06 eV). This experiment also provides reliable values for the vibrational spacing [ΔG(1/2)=859.5±0.5 cm-1], rotational constants (Be+=0.6395±0.0018 cm-1 and αe+=0.0097±0.0009 cm-1), and equilibrium bond distance (re+=1.628 Å) for the NiC+(X Σ2+) ground state. The experimental results presented here are valuable for benchmarking the development of more reliable ab initio quantum computation procedures for energetic and spectroscopic calculations of transition metal-containing molecules.

  5. PHOTOIONIZATION OF HIGH-ALTITUDE GAS IN A SUPERNOVA-DRIVEN TURBULENT INTERSTELLAR MEDIUM

    SciTech Connect

    Wood, Kenneth; Hill, Alex S.; Haffner, L. Matthew; Reynolds, R. J.; Joung, M. Ryan; Mac Low, Mordecai-Mark; Benjamin, Robert A.; Madsen, G. J.

    2010-10-01

    We investigate models for the photoionization of the widespread diffuse ionized gas (DIG) in galaxies. In particular, we address the long standing question of the penetration of Lyman continuum photons from sources close to the galactic midplane to large heights in the galactic halo. We find that recent hydrodynamical simulations of a supernova-driven interstellar medium (ISM) have low-density paths and voids that allow for ionizing photons from midplane OB stars to reach and ionize gas many kiloparsecs above the midplane. We find that ionizing fluxes throughout our simulation grids are larger than predicted by one-dimensional slab models, thus allowing for photoionization by O stars of low altitude neutral clouds in the Galaxy that are also detected in H{alpha}. In previous studies of such clouds, the photoionization scenario had been rejected and the H{alpha} had been attributed to enhanced cosmic ray ionization or scattered light from midplane H II regions. We do find that the emission measure distributions in our simulations are wider than those derived from H{alpha} observations in the Milky Way. In addition, the horizontally averaged height dependence of the gas density in the hydrodynamical models is lower than inferred in the Galaxy. These discrepancies are likely due to the absence of magnetic fields in the hydrodynamic simulations and we discuss how magnetohydrodynamic effects may reconcile models and observations. Nevertheless, we anticipate that the inclusion of magnetic fields in the dynamical simulations will not alter our primary finding that midplane OB stars are capable of producing high-altitude DIG in a realistic three-dimensional ISM.

  6. Multimodal optical molecular image reconstruction with frequency domain measurements.

    PubMed

    Bartels, M; Chen, W; Bardhan, R; Ke, S; Halas, N J; Wareing, T; McGhee, J; Joshi, A

    2009-01-01

    Multimodality molecular imaging is becoming more and more important to understand both the structural and the functional characteristics of tissue, organs and tumors. So far, invasive nuclear methods utilizing ionizing radiation have been the "gold standard" of molecular imaging. We investigate non-contact, non-invasive, patient-tolerant and inexpensive near infrared (NIR) frequency domain optical tomography (FDOT) as a functional complement to structural X-ray computed tomography (CT) data. We show a novel multifrequency NIR FDOT approach both in transmission and reflectance mode and employ radiative transport equation (RTE) for 3D reconstruction of a target with novel fluorescent gold nanoshell indocyanine green (NS ICG) in an ex vivo nude mouse. The results demonstrate that gold NS ICG with multifrequency NIR FDOT is a promising fluorophore for multimodal optical molecular image reconstruction.

  7. Low temperature plasmas created by photoionization of gases with intense radiation pulses from laser-produced plasma sources

    NASA Astrophysics Data System (ADS)

    Bartnik, A.; Pisarczyk, T.; Wachulak, P.; Chodukowski, T.; Fok, T.; Wegrzyński, Ł.; Kalinowska, Z.; Fiedorowicz, H.

    2016-12-01

    A comparative study of photoionized plasmas created by soft X-ray (SXR) and extreme ultraviolet (EUV) laser plasma sources was performed. The sources, employing high or low energy laser systems, utilized double-stream Xe/He gas-puff targets irradiated with laser pulses of different parameters. The SXR/EUV beams were used for irradiation of a gas stream, injected into a vacuum chamber synchronously with the radiation pulse. Photoionized plasmas produced this way in Ne gas emitted radiation in the SXR/EUV range. The corresponding spectra were dominated by emission lines originating from singly charged ions. Significant differences between spectra obtained in different experimental conditions concern specific transitions in Ne II ions. Creation of photoionized plasmas by SXR or EUV irradiation resulted in K-shell or L-shell emissions respectively. In case of the low energy system absorption spectra were measured additionally. In case of the high energy system, the electron density measurements were performed by laser interferometry, employing a femtosecond laser system. A maximum electron density reached the value of 2·1018cm-3. For the low energy system, a detection limit was too high for the interferometric measurements, thus only an upper estimation for electron density could be made.

  8. VUV photoionization and dissociative photoionization of the prebiotic molecule acetyl cyanide: Theory and experiment

    SciTech Connect

    Bellili, A.; Hochlaf, M. E-mail: martin.schwell@lisa.u-pec.fr; Schwell, M. E-mail: martin.schwell@lisa.u-pec.fr; Bénilan, Y.; Fray, N.; Gazeau, M.-C.; Mogren Al-Mogren, M.; Guillemin, J.-C.; Poisson, L.

    2014-10-07

    The present combined theoretical and experimental investigation concerns the single photoionization of gas-phase acetyl cyanide and the fragmentation pathways of the resulting cation. Acetyl cyanide (AC) is inspired from both the chemistry of cyanoacetylene and the Strecker reaction which are thought to be at the origin of medium sized prebiotic molecules in the interstellar medium. AC can be formed by reaction from cyanoacetylene and water but also from acetaldehyde and HCN or the corresponding radicals. In view of the interpretation of vacuum ultraviolet (VUV) experimental data obtained using synchrotron radiation, we explored the ground potential energy surface (PES) of acetyl cyanide and of its cation using standard and recently implemented explicitly correlated methodologies. Our PES covers the regions of tautomerism (between keto and enol forms) and of the lowest fragmentation channels. This allowed us to deduce accurate thermochemical data for this astrobiologically relevant molecule. Unimolecular decomposition of the AC cation turns out to be very complex. The implications for the evolution of prebiotic molecules under VUV irradiation are discussed.

  9. VUV photoionization and dissociative photoionization of the prebiotic molecule acetyl cyanide: Theory and experiment

    NASA Astrophysics Data System (ADS)

    Bellili, A.; Schwell, M.; Bénilan, Y.; Fray, N.; Gazeau, M.-C.; Mogren Al-Mogren, M.; Guillemin, J.-C.; Poisson, L.; Hochlaf, M.

    2014-10-01

    The present combined theoretical and experimental investigation concerns the single photoionization of gas-phase acetyl cyanide and the fragmentation pathways of the resulting cation. Acetyl cyanide (AC) is inspired from both the chemistry of cyanoacetylene and the Strecker reaction which are thought to be at the origin of medium sized prebiotic molecules in the interstellar medium. AC can be formed by reaction from cyanoacetylene and water but also from acetaldehyde and HCN or the corresponding radicals. In view of the interpretation of vacuum ultraviolet (VUV) experimental data obtained using synchrotron radiation, we explored the ground potential energy surface (PES) of acetyl cyanide and of its cation using standard and recently implemented explicitly correlated methodologies. Our PES covers the regions of tautomerism (between keto and enol forms) and of the lowest fragmentation channels. This allowed us to deduce accurate thermochemical data for this astrobiologically relevant molecule. Unimolecular decomposition of the AC cation turns out to be very complex. The implications for the evolution of prebiotic molecules under VUV irradiation are discussed.

  10. Modeling the heating and atomic kinetics of a photoionized neon plasma experiment

    NASA Astrophysics Data System (ADS)

    Lockard, Tom E.

    Motivated by gas cell photoionized plasma experiments performed by our group at the Z facility of Sandia National Laboratories, we discuss in this dissertation a modeling study of the heating and ionization of the plasma for conditions characteristic of these experiments. Photoionized plasmas are non-equilibrium systems driven by a broadband x-ray radiation flux. They are commonly found in astrophysics but rarely seen in the laboratory. Several modeling tools have been employed: (1) a view-factor computer code constrained with side x-ray power and gated monochromatic image measurements of the z-pinch radiation, to model the time-history of the photon-energy resolved x-ray flux driving the photoionized plasma, (2) a Boltzmann self-consistent electron and atomic kinetics model to simulate the electron distribution function and configuration-averaged atomic kinetics, (3) a radiation-hydrodynamics code with inline non-equilibrium atomic kinetics to perform a comprehensive numerical simulation of the experiment and plasma heating, and (4) steady-state and time-dependent collisional-radiative atomic kinetics calculations with fine-structure energy level description to assess transient effects in the ionization and charge state distribution of the plasma. The results indicate that the photon-energy resolved x-ray flux impinging on the front window of the gas cell is very well approximated by a linear combination of three geometrically-diluted Planckian distributions. Knowledge of the spectral details of the x-ray drive turned out to be important for the heating and ionization of the plasma. The free electrons in the plasma thermalize quickly relative to the timescales associated with the time-history of the x-ray drive and the plasma atomic kinetics. Hence, electrons are well described by a Maxwellian energy distribution of a single temperature. This finding is important to support the application of a radiation-hydrodynamic model to simulate the experiment. It is found

  11. Quantitation of Interacting Molecular Species and Measurement of Molecular Avidity by Single Radial (Immuno) Diffusion

    DTIC Science & Technology

    1989-09-01

    FIGURE LEGEND 1lL ;Ta ,j - ’V y ilii INTRODUCTION Mancini et al. (1965) developed a single radial immunodiffusion (SRID) method for the quantitation of...quantitation of antigens by single radial immunodiffusion . Immunochem, 2, 5. Mancini , G., Nash, D. R. and Heremans, J. F. (1970) Further studies on...FIELD GROUP SUB-GROUP Single radial immunodiffusion , Single radial diffusion, Molecular interaction, Molecular avidity, endotoxin ’-." 19 A63TRACT

  12. X-ray and EUV spectroscopy of various astrophysical and laboratory plasmas: Collisional, photoionization and charge-exchange plasmas

    SciTech Connect

    Liang, G. Y.; Li, F.; Wang, F. L.; Zhong, J. Y.; Zhao, G.; Wu, Y.

    2014-03-10

    Several laboratory facilities were used to benchmark theoretical spectral models that are extensively used by astronomical communities. However, there are still many differences between astrophysical environments and laboratory miniatures that can be archived. Here we setup a spectral analysis system for astrophysical and laboratory plasmas to make a bridge between them, and we investigate the effects from non-thermal electrons and the contributions from a metastable level population on level populations and charge stage distribution for coronal-like, photoionized, and geocoronal plasmas. Test applications to laboratory measurement (i.e., electron beam ion trap plasma) and astrophysical observation (i.e., Comet, Cygnus X-3) are presented. A time evolution of the charge stage and level population are also explored for collisional and photoionized plasmas.

  13. Direct observation of Young’s double-slit interferences in vibrationally resolved photoionization of diatomic molecules

    PubMed Central

    Canton, Sophie E.; Plésiat, Etienne; Bozek, John D.; Rude, Bruce S.; Decleva, Piero; Martín, Fernando

    2011-01-01

    Vibrationally resolved valence-shell photoionization spectra of H2, N2 and CO have been measured in the photon energy range 20–300 eV using third-generation synchrotron radiation. Young’s double-slit interferences lead to oscillations in the corresponding vibrational ratios, showing that the molecules behave as two-center electron-wave emitters and that the associated interferences leave their trace in the angle-integrated photoionization cross section. In contrast to previous work, the oscillations are directly observable in the experiment, thereby removing any possible ambiguity related to the introduction of external parameters or fitting functions. A straightforward extension of an original idea proposed by Cohen and Fano [Cohen HD, Fano U (1966) Phys Rev 150:30] confirms this interpretation and shows that it is also valid for diatomic heteronuclear molecules. Results of accurate theoretical calculations are in excellent agreement with the experimental findings.

  14. Study on photoionization in a rubidium diode-pumped alkali laser gain medium with the optogalvanic method.

    PubMed

    Ge, Lun; Hua, Weihong; Wang, Hongyan; Yang, Zining; Xu, Xiaojun

    2013-01-15

    We use the optogalvanic method to calculate the concentration of rubidium ions produced by photoionization in a Rb diode-pumped alkali laser gain medium. With bias voltage added across the electrodes of a rubidium hollow cathode lamp, the measured optogalvanic current is 2.3×10(-7) A. Further study shows that the rubidium ion concentration is proportional to the pump intensity, and the drift velocity of rubidium ions is proportional to the bias voltage. When the photoionization process reaches dynamic equilibrium, the rubidium ion concentration will not increase with growing rubidium atom density. The calculated rubidium ion concentration is 1.5×10(5)-10(6) according to the experiment, and the ionization degree is less than 2.4×10(-7).

  15. Low-energy fine-structure resonances in photoionization of O ii

    NASA Astrophysics Data System (ADS)

    Nahar, Sultana N.; Montenegro, Maximiliano; Eissner, Werner; Pradhan, Anil K.

    2010-12-01

    Resonant features in low-energy photoionization cross sections are reported in coupled-channel calculations for O ii including relativistic fine structure. The calculations reveal extensive near-threshold resonant structures in the small energy region between the fine structure levels of the ground state 2p2(3P0,1,2) of the residual ion O iii. Although the resonances have not yet been observed, they are similar to other experimentally observed features. They are expected to significantly enhance the very-low-temperature dielectronic recombination rates, potentially leading to the resolution of an outstanding nebular abundances anomaly. Higher energy partial and total photoionization cross sections of the ground configuration levels 2p3(4S3/2o,2D3/2,5/2o,2P1/2,3/2o) are found to be in agreement with experimental measurements on synchrotron-based photon sources [1-3], thereby identifying the excited O iii levels present in the ion beams. These are also the first results from a recently developed version of Breit-Pauli R-matrix (BPRM) codes, with inclusion of two-body magnetic interaction terms. The improved relativistic treatment could be important for other astrophysical applications and for more precise benchmarking of experimental measurements.

  16. Partial and total cross sections and multiplet structure in the photoionization of atomic manganese

    SciTech Connect

    Jimenez-Mier, J.; Krause, M.O.; Gerard, P. ); Hermsmeier, B.; Fadley, C.S.

    1989-10-01

    We determined the absolute partial photoionization cross section {sigma} and the angular distribution parameter {beta} of the 3{ital d}, 3{ital p}, and 3{ital s} photoelectrons in atomic manganese for 65{le}{ital h}{nu}{le}250 eV. The total photoionization cross section is in satisfactory accord with the single-particle Hartree-Slater calculation and in very good agreement with a relativistic time-dependent local-density-approximation calculation. Binding energies and intensity ratios of the 3{ital s}{sup {minus}1} and 3{ital p}{sup {minus}1} multiplet lines were obtained. Five lines were identified within the 3{ital p}{sup {minus}1} multiplet, and the measured spacings are close to those found in solid MnF{sub 2}. Similarly, the spacings in the 3{ital s}{sup {minus}1} multiplet are equal to the ones measured in solid MnF{sub 2}. There is good accord between our results for the angular-distribution parameter of the 3{ital p}{sup {minus}1} ({sup 7}P) line and those of Malutzki {ital et} {ital al}. (J. Phys. B 18, 1735 (1985)). The intensity ratios of {sup 5}P(1) to {sup 7}P and {sup 5}S(1) to {sup 7}S were seen to increase slowly somewhat above their thresholds. More rapid variations of all multiplet ratios were found within about 30 eV of threshold.

  17. Low-energy fine-structure resonances in photoionization of O ii

    SciTech Connect

    Nahar, Sultana N.; Pradhan, Anil K.; Montenegro, Maximiliano; Eissner, Werner

    2010-12-15

    Resonant features in low-energy photoionization cross sections are reported in coupled-channel calculations for O ii including relativistic fine structure. The calculations reveal extensive near-threshold resonant structures in the small energy region between the fine structure levels of the ground state 2p{sup 2}({sup 3}P{sub 0,1,2}) of the residual ion O iii. Although the resonances have not yet been observed, they are similar to other experimentally observed features. They are expected to significantly enhance the very-low-temperature dielectronic recombination rates, potentially leading to the resolution of an outstanding nebular abundances anomaly. Higher energy partial and total photoionization cross sections of the ground configuration levels 2p{sup 3}({sup 4}S{sub 3/2}{sup o},{sup 2}D{sub 3/2,5/2}{sup o},{sup 2}P{sub 1/2,3/2}{sup o}) are found to be in agreement with experimental measurements on synchrotron-based photon sources [1-3], thereby identifying the excited O iii levels present in the ion beams. These are also the first results from a recently developed version of Breit-Pauli R-matrix (BPRM) codes, with inclusion of two-body magnetic interaction terms. The improved relativistic treatment could be important for other astrophysical applications and for more precise benchmarking of experimental measurements.

  18. Theoretical Studies of Starburst Infrared Emission: Luminosity Indicators in Dusty Photoionized Environments

    NASA Technical Reports Server (NTRS)

    Bottorff, Mark; LaMothe, Joseph; Momjian, Emmanuel; Verner, Ekaterina; Vinkovic, Dejan; Ferland, Gary J.

    1998-01-01

    The luminosity of the central source in ionizing radiation is an essential parameter in a photoionized environment and is one of the most fundamental physical quantities one can measure. We outline a method of determining the luminosity for any emission-line region using only infrared data. In dusty environments, grains compete with hydrogen in absorbing continuum radiation. Grains produce infrared emission, and hydrogen produces recombination lines. We have computed a very large variety of photoionization models, using ranges of abundances, grain mixtures, ionizing continua, densities, and ionization parameters. The conditions were appropriate for such diverse objects as H(II) regions, planetary nebulae, starburst galaxies, and the narrow- and broad-line regions of active nuclei. The ratio of the total thermal grain emission relative to H-Beta (IR/H-Beta) is the primary indicator of whether the cloud behaves as a classical Stroemgren sphere (a hydrogen-bounded nebula) or whether grains absorb most of the incident continuum (a dust-bounded nebula). We find two global limits: when IR/H-Beta < 100, infrared recombination lines determine the source luminosity in ionizing photons; when IR/H-Beta >> 100, the grains act as a bolometer to measure the luminosity.

  19. System Concept for Remote Measurement of Asteroid Molecular Composition

    NASA Astrophysics Data System (ADS)

    Hughes, G. B.; Lubin, P. M.; Zhang, Q.; Brashears, T.; Cohen, A. N.; Madajian, J.

    2016-12-01

    We propose a method for probing the molecular composition of cold solar system targets (asteroids, comets, planets, moons) from a distant vantage, such as from a spacecraft orbiting the object. A directed energy beam is focused on the target. With sufficient flux, the spot temperature rises rapidly, and evaporation of surface materials occurs. The melted spot creates a high-temperature blackbody source, and ejected material creates a plume of surface materials in front of the spot. Molecular and atomic absorption of the blackbody radiation occurs within the ejected plume. Bulk composition of the surface material is investigated by using a spectrometer to view the heated spot through the ejected material. Our proposed method differs from technologies such as Laser-Induced Breakdown Spectroscopy (LIBS), which atomizes and ionizes materials in the target; scattered ions emit characteristic radiation, and the LIBS detector performs atomic composition analysis by observing emission spectra. Standoff distance for LIBS is limited by the strength of characteristic emission, and distances greater than 10 m are problematic. Our proposed method detects atomic and molecular absorption spectra in the plume; standoff distance is limited by the size of heated spot, and the plume opacity; distances on the order of tens of kilometers are immediately feasible. Simulations have been developed for laser heating of a rocky target, with concomitant evaporation. Evaporation rates lead to determination of plume density and opacity. Absorption profiles for selected materials are estimated from plume properties. Initial simulations of absorption profiles with laser heating show great promise for molecular composition analysis from tens of kilometers distance. This paper explores the feasibility a hypothetical mission that seeks to perform surface molecular composition analysis of a near-earth asteroid while the craft orbits the asteroid. Such a system has compelling potential benefit for

  20. Converged cross-section results for double photoionization of helium atoms in hyperspherical partial wave theory at 6 eV above threshold

    SciTech Connect

    Das, J.N.; Paul, S.; Chakrabarti, K.

    2004-04-01

    Here we report a set of converged cross-section results for double photoionization of helium atoms obtained in the hyperspherical partial wave theory for equal energy sharing kinematics at 6 eV energy above threshold. The calculated cross section results are generally in excellent agreement with the absolute measured results of Doerner et al. [Phys. Rev. 57, 1074 (1998)].

  1. High-gain inner-shell photoionization laser in Cd vapor pumped by soft-x-ray radiation from a laser-produced plasma source.

    PubMed

    Silfvast, W T; Macklin, J J; Ii, O R

    1983-11-01

    A soft-x-ray-pumped inner-shell photoionization laser has been produced in Cd vapor at 4416 and 3250 A. A gain of 5.6 cm(-1) has been measured at 4416 A, and a reasonably high-energy storage of 0.2 mJ/cm(3) in the upper laser states has been obtained.

  2. Multiconfigurational Hartree-Fock close-coupling ansatz: Application to the argon photoionization cross section and delays

    NASA Astrophysics Data System (ADS)

    Carette, T.; Dahlström, J. M.; Argenti, L.; Lindroth, E.

    2013-02-01

    We present a robust, ab initio method for addressing atom-light interactions and apply it to photoionization of argon. We use a close-coupling ansatz constructed on a multiconfigurational Hartree-Fock description of localized states and B-spline expansions of the electron radial wave functions. In this implementation, the general many-electron problem can be tackled thanks to the use of the atsp2k libraries [C. Froese Fischer , Comput. Phys. Commun.CPHCBZ0010-465510.1016/j.cpc.2007.01.006 176, 559 (2007)]. In the present contribution, we combine this method with exterior complex scaling, thereby allowing for the computation of the complex partial amplitudes that encode the whole dynamics of the photoionization process. The method is validated on the 3s3p6np series of resonances converging to the 3s extraction. Then, it is used for computing the energy dependent differential atomic delay between 3p and 3s photoemission, and agreement is found with the measurements of Guénot [Phys. Rev. APLRAAN1050-294710.1103/PhysRevA.85.053424 85, 053424 (2012)]. The effect of the presence of resonances in the one-photon spectrum on photoionization delay measurements is studied.

  3. Kinetic temperature of massive star-forming molecular clumps measured with formaldehyde. II. The Large Magellanic Cloud

    NASA Astrophysics Data System (ADS)

    Tang, X. D.; Henkel, C.; Chen, C.-H. R.; Menten, K. M.; Indebetouw, R.; Zheng, X. W.; Esimbek, J.; Zhou, J. J.; Yuan, Y.; Li, D. L.; He, Y. X.

    2017-04-01

    Context. The kinetic temperature of molecular clouds is a fundamental physical parameter affecting star formation and the initial mass function. The Large Magellanic Cloud (LMC) is the closest star-forming galaxy with a low metallicity and provides an ideal laboratory for studying star formation in such an environment. Aims: The classical dense molecular gas thermometer NH3 is seldom available in a low-metallicity environment because of photoionization and a lack of nitrogen atoms. Our goal is to directly measure the gas kinetic temperature with formaldehyde toward six star-forming regions in the LMC. Methods: Three rotational transitions (JKAKC = 303-202, 322-221, and 321-220) of para-H2CO near 218 GHz were observed with the Atacama Pathfinder EXperiment (APEX) 12 m telescope toward six star-forming regions in the LMC. These data are complemented by C18O 2-1 spectra. Results: Using non-local thermal equilibrium modeling with RADEX, we derive the gas kinetic temperature and spatial density, using as constraints the measured para-H2CO 321-220/303-202 and para-H2CO 303-202/C18O 2-1 ratios. Excluding the quiescent cloud N159S, where only one para-H2CO line could be detected, the gas kinetic temperatures derived from the preferred para-H2CO 321-220/303-202 line ratios range from 35 to 63 K with an average of 47 ± 5 K (errors are unweighted standard deviations of the mean). Spatial densities of the gas derived from the para-H2CO 303-202/C18O 2-1 line ratios yield 0.4-2.9 × 105 cm-3 with an average of 1.5 ± 0.4 × 105 cm-3. Temperatures derived from the para-H2CO line ratio are similar to those obtained with the same method from Galactic star-forming regions and agree with results derived from CO in the dense regions (n(H2) > 103 cm-3) of the LMC. A comparison of kinetic temperatures derived from para-H2CO with those from the dust also shows good agreement. This suggests that the dust and para-H2CO are well mixed in the studied star-forming regions. A comparison of

  4. Single-center model for double photoionization of the H{sub 2} molecule

    SciTech Connect

    Kheifets, A.S.

    2005-02-01

    We present a single-center model of double photoionization (DPI) of the H{sub 2} molecule which combines a multiconfiguration expansion of the molecular ground state with the convergent close-coupling description of the two-electron continuum. Because the single-center final-state wave function is only correct in the asymptotic region of large distances, the model cannot predict the magnitude of the DPI cross sections. However, we expect the model to account for the angular correlation in the two-electron continuum and to reproduce correctly the shape of the fully differential DPI cross sections. We test this assumption in kinematics of recent DPI experiments on the randomly oriented and fixed in space hydrogen molecule in the isotopic form of D{sub 2}.

  5. Synchrotron photoionization mass spectrometry study of intermediates in fuel-rich 1,2-dimethoxyethane flame

    SciTech Connect

    Lin, Z. K.; Han, D. L.; Li, S. F.; Li, Y. Y.; Yuan, T.

    2009-04-21

    Intermediates in a fuel-rich premixed laminar 1,2-dimethoxyethane (DME) flame are studied by molecular beam mass spectrometry combined with tunable synchrotron vacuum ultraviolet photoionization. About 30 intermediate species are identified in the present work, and their mole fraction profiles are evaluated. The experimental results show that the formations of intermediates, both hydrocarbons and oxygenated hydrocarbons, are closely linked to the structure of fuel, which is consistent with the previous reports. Species produced from H atom abstraction and beta scission of DME usually have much higher concentrations than others. The oxygen atoms in DME are considered to act as partitions of the primary intermediates; therefore farther reactions among these primary intermediates are difficult to occur, resulting in absence of most large intermediate species.

  6. Laser-Induced Acoustic Desorption Atmospheric Pressure Photoionization via VUV-Generating Microplasmas.

    PubMed

    Benham, Kevin; Hodyss, Robert; Fernández, Facundo M; Orlando, Thomas M

    2016-11-01

    We demonstrate the first application of laser-induced acoustic desorption (LIAD) and atmospheric pressure photoionization (APPI) as a mass spectrometric method for detecting low-polarity organics. This was accomplished using a Lyman-α (10.2 eV) photon generating microhollow cathode discharge (MHCD) microplasma photon source in conjunction with the addition of a gas-phase molecular dopant. This combination provided a soft desorption and a relatively soft ionization technique. Selected compounds analyzed include α-tocopherol, perylene, cholesterol, phenanthrene, phylloquinone, and squalene. Detectable surface concentrations as low as a few pmol per spot sampled were achievable using test molecules. The combination of LIAD and APPI provided a soft desorption and ionization technique that can allow detection of labile, low-polarity, structurally complex molecules over a wide mass range with minimal fragmentation. Graphical Abstract ᅟ.

  7. Photoionization of atoms confined in C60 versus C240: Giant enhancement and attosecond delay

    NASA Astrophysics Data System (ADS)

    Magrakvelidze, Maia; Shi, Kele; Anstine, Dylan; Chakraborty, Himadri

    2015-05-01

    We investigate the effects of confinement and electron correlation on the photoemissions of noble gas atoms sequestered endohedrally in C60 versus C240. The time-dependent local density approximation (TDLDA) method with Leeuwen and Baerends (LB94) exchange-correlation functional is employed. We study the moduli and phases of the photoionization dipole matrix elements involving atomic-type as well as atom-fullerene hybrid-type levels of the molecules and extract associated cross sections and angle-integrated Wigner-Smith time-delays. We examine the size effects of the molecular cage on the plasmonically enhanced strength of the atomic ionization. Furthermore, the behavior of emission time delays in attoseconds, induced by this enhancement as well as by the confinement-modified atomic Cooper minima, as a function of fullerene size is scrutinized in detailed. This work was supported by the U.S. National Science Foundation.

  8. Intense-Field Photoionization of Molecules using Ultrashort Radiation Pulses: Carbon Disulfide and Carbon Dioxide

    NASA Astrophysics Data System (ADS)

    Beck, Joshua; Uiterwaal, Cornelis

    2016-05-01

    We experimentally investigate the photoionization and photofragmentation of molecules using intense fields from an 800 nm, femtosecond laser source and an experimental method that eliminates the focal volume effect without the need for data deconvolution. Targets include carbon disulfide and carbon dioxide. We show that ionization is insignificant for intensities that maximize alignment of carbon disulfide, which validates ultrafast electron diffraction experiments from aligned carbon disulfide. For comparison, we also investigate the analogous molecule carbon dioxide. In this molecule the molecular bonding orbitals include the n = 2 atomic orbitals of the oxygen atom, while in carbon disulfide the n = 3 orbitals of the sulfur atom contribute to the bonding. Recent work will be presented. This work supported by U.S. Dept. of Education GAANN Grants Nos. P200A090156 and P200A120188 and National Science Foundation EPSCoR RII Track-2 CA Award No. IIA-1430519 (Cooperative Nebraska-Kansas Grant).

  9. Photoionization and ion cyclotron resonance studies of the ion chemistry of ethylene oxide

    NASA Technical Reports Server (NTRS)

    Corderman, R. R.; Williamson, A. D.; Lebreton, P. R.; Buttrill, S. E., Jr.; Beauchamp, J. L.

    1976-01-01

    The formation of the ethylene oxide molecular ion and its subsequent ion-molecule reactions leading to the products C2H5O(+) and C3H5O(+) have been studied using time-resolved photoionization mass spectroscopy, ion cyclotron resonance spectroscopy, and photoelectron spectroscopy. An examination of the effects of internal energy on reactivity shows that the ratio of C3H5O(+) to C2H5O(+) increases by an order of magnitude with a single quantum of vibrational energy. The formation of (C2H4O/+/)-asterisk in a collision-induced isomerization is found which yields a ring-opened structure by C-C bond cleavage. The relaxed ring-opened C2H4O(+) ion reacts with neutral ethylene oxide by CH2(+) transfer to yield an intermediate product ion C3H6O(+) which gives C3H5O(+) by loss of H.

  10. Laser-Induced Acoustic Desorption Atmospheric Pressure Photoionization via VUV-Generating Microplasmas

    NASA Astrophysics Data System (ADS)

    Benham, Kevin; Hodyss, Robert; Fernández, Facundo M.; Orlando, Thomas M.

    2016-11-01

    We demonstrate the first application of laser-induced acoustic desorption (LIAD) and atmospheric pressure photoionization (APPI) as a mass spectrometric method for detecting low-polarity organics. This was accomplished using a Lyman-α (10.2 eV) photon generating microhollow cathode discharge (MHCD) microplasma photon source in conjunction with the addition of a gas-phase molecular dopant. This combination provided a soft desorption and a relatively soft ionization technique. Selected compounds analyzed include α-tocopherol, perylene, cholesterol, phenanthrene, phylloquinone, and squalene. Detectable surface concentrations as low as a few pmol per spot sampled were achievable using test molecules. The combination of LIAD and APPI provided a soft desorption and ionization technique that can allow detection of labile, low-polarity, structurally complex molecules over a wide mass range with minimal fragmentation.

  11. Synchrotron photoionization mass spectrometry study of intermediates in fuel-rich 1,2-dimethoxyethane flame

    NASA Astrophysics Data System (ADS)

    Lin, Z. K.; Han, D. L.; Li, S. F.; Li, Y. Y.; Yuan, T.

    2009-04-01

    Intermediates in a fuel-rich premixed laminar 1,2-dimethoxyethane (DME) flame are studied by molecular beam mass spectrometry combined with tunable synchrotron vacuum ultraviolet photoionization. About 30 intermediate species are identified in the present work, and their mole fraction profiles are evaluated. The experimental results show that the formations of intermediates, both hydrocarbons and oxygenated hydrocarbons, are closely linked to the structure of fuel, which is consistent with the previous reports. Species produced from H atom abstraction and beta scission of DME usually have much higher concentrations than others. The oxygen atoms in DME are considered to act as partitions of the primary intermediates; therefore farther reactions among these primary intermediates are difficult to occur, resulting in absence of most large intermediate species.

  12. Quantum signatures of a molecular nanomagnet in direct magnetocaloric measurements.

    PubMed

    Sharples, Joseph W; Collison, David; McInnes, Eric J L; Schnack, Jürgen; Palacios, Elias; Evangelisti, Marco

    2014-10-22

    Geometric spin frustration in low-dimensional materials, such as the two-dimensional kagome or triangular antiferromagnetic nets, can significantly enhance the change of the magnetic entropy and adiabatic temperature following a change in the applied magnetic field, that is, the magnetocaloric effect. In principle, an equivalent outcome should also be observable in certain high-symmetry zero-dimensional, that is, molecular, structures with frustrated topologies. Here we report experimental realization of this in a heptametallic gadolinium molecule. Adiabatic demagnetization experiments reach ~200 mK, the first sub-Kelvin cooling with any molecular nanomagnet, and reveal isentropes (the constant entropy paths followed in the temperature-field plane) with a rich structure. The latter is shown to be a direct manifestation of the trigonal antiferromagnetic net structure, allowing study of frustration-enhanced magnetocaloric effects in a finite system.

  13. Analysis of 62 synthetic cannabinoids by gas chromatography-mass spectrometry with photoionization.

    PubMed

    Akutsu, Mamoru; Sugie, Ken-Ichi; Saito, Koichi

    2017-01-01

    Gas chromatography-mass spectrometry (GC-MS) in electron ionization (EI) mode is one of the most commonly used techniques for analysis of synthetic cannabinoids, because the GC-EI-MS spectra contain characteristic fragment ions for identification of a compound; however, the information on its molecular ions is frequently lacking. To obtain such molecular ion information, GC-MS in chemical ionization (CI) mode is frequently used. However, GC-CI-MS requires a relatively tedious process using reagent gas such as methane or isobutane. In this study, we show that GC-MS in photoionization (PI) mode provided molecular ions in all spectra of 62 synthetic cannabinoids, and 35 of the 62 compounds showed only the molecular radical cations. Except for the 35 compounds, the PI spectra showed very simple patterns with the molecular peak plus only a few fragment peak(s). An advantage is that the ion source for GC-PI-MS can easily be used for GC-EI-MS as well. Therefore, GC-EI/PI-MS will be a useful tool for the identification of synthetic cannabinoids contained in a dubious product. To the best of our knowledge, this is the first report to use GC-PI-MS for analysis of synthetic cannabinoids.

  14. Time-Dependent Photoionization of Gas Outflows in AGN

    NASA Astrophysics Data System (ADS)

    Elhoussieny, Ehab E.; Bautista, M.; Garcia, J.; Kallman, T. R.

    2013-01-01

    Gas outflows are fundamental components of Active Galactic Nuclei (AGN) activity. Time-variability of ionizing radiation, which is characteristic of AGN in various different time scales, may produce non-equilibrium photoionization conditions over a significant fraction of the flow and yields supersonically moving cooling/heating fronts. These fast fronts create pressure imbalances that can only be resolved by fragmentation of the flow and acceleration of such fragments. This mechanism can explain the kinematic structure of low ionization BAL systems (FeLoBAL). This mechanism may also have significant effects on other types of outflows given the wide range of variability time scales in AGN. We will study these effects in detail by constructing time-dependent photoionization models of the outflows and incorporating these models into radiative-hydrodynamic simulations.

  15. Photoionization of Endohedral Atoms: Collective, Reflective and Collateral Emissions

    NASA Astrophysics Data System (ADS)

    Chakraborty, Himadri S.; McCune, Matthew A.; Madjet, Mohamed E.; Hopper, Dale E.; Manson, Steven T.

    2009-12-01

    The photoionization properties of a fullerene-confined atom differ dramatically from that of an isolated atom. In the low energy region, where the fullerene plasmons are active, the electrons of the confined atom emerge through a collective channel carrying a significant chunk of plasmon with it. The photoelectron angular distribution of the confined atom however shows far lesser impact of the effect. At higher energies, the interference between two single-electron ionization channels, one directly from the atom and another reflected off the fullerene cage, producuces oscillatory cross sections. But for the outermost atomic level, which transfers some electrons to the cage, oscillations are further modulated by the collateral emission from the part of the atomic charge density transferred to the cage. These various modes of emissions are studied for the photoionization of Ar endohedrally confined in C60.

  16. K -shell double photoionization of Be, Mg, and Ca

    NASA Astrophysics Data System (ADS)

    Kheifets, A. S.; Bray, Igor; Hoszowska, J.

    2009-04-01

    We perform convergent close-coupling calculations of double photoionization (DPI) of the K -shell of alkaline-earth metal atoms (Be, Mg, and Ca) from the threshold to the nonrelativistic limit of infinite photon energy. Theoretical double-to-single photoionization cross-section ratios for Mg and Ca are compared with experimental values derived from high-resolution x-ray spectra following the radiative decay of the K -shell double vacancy. We investigate the role of many-electron correlations in the ground and doubly-ionized final states played in the DPI process. Universal scaling of DPI cross section with an effective nuclear charge is examined in neutral atoms in comparison with corresponding heliumlike ions.

  17. Double Photoionization into Double Core-Hole States in Xe

    SciTech Connect

    Hikosaka, Y.; Kaneyasu, T.; Shigemasa, E.; Lablanquie, P.; Penent, F.; Eland, J. H. D.; Aoto, T.; Ito, K.

    2007-05-04

    Double photoionization (DPI) leading to double core-hole states of Xe{sup 2+} 4d{sup -2} has been studied using a magnetic bottle time-of-flight spectrometer. The assignments of the Xe{sup 2+} 4d{sup -2} states are confirmed by the Auger lines extracted from fourfold coincidences including two photoelectrons and two Auger electrons. It is estimated that the core-core DPI into Xe{sup 2+} 4d{sup -2} at a photon energy of 301.6 eV has a favored cross section of about 0.3 MB. The intense core-core DPI is due to mixing of the 4d{sup -2} continuum with the 4p single photoionization, which is manifested in the relative intensities of the Xe{sup 2+} 4d{sup -2} components.

  18. Communication: The influence of vibrational parity in chiral photoionization dynamics

    SciTech Connect

    Powis, Ivan

    2014-03-21

    A pronounced vibrational state dependence of photoelectron angular distributions observed in chiral photoionization experiments is explored using a simple, yet realistic, theoretical model based upon the transiently chiral molecule H{sub 2}O{sub 2}. The adiabatic approximation is used to separate vibrational and electronic wavefunctions. The full ionization matrix elements are obtained as an average of the electronic dipole matrix elements over the vibrational coordinate, weighted by the product of neutral and ion state vibrational wavefunctions. It is found that the parity of the vibrational Hermite polynomials influences not just the amplitude, but also the phase of the transition matrix elements, and the latter is sufficient, even in the absence of resonant enhancements, to account for enhanced vibrational dependencies in the chiral photoionization dynamics.

  19. Spatially resolved photoionization of ultracold atoms on an atom chip

    SciTech Connect

    Kraft, S.; Guenther, A.; Fortagh, J.; Zimmermann, C.

    2007-06-15

    We report on photoionization of ultracold magnetically trapped Rb atoms on an atom chip. The atoms are trapped at 5 {mu}K in a strongly anisotropic trap. Through a hole in the chip with a diameter of 150 {mu}m, two laser beams are focused onto a fraction of the atomic cloud. A first laser beam with a wavelength of 778 nm excites the atoms via a two-photon transition to the 5D level. With a fiber laser at 1080 nm the excited atoms are photoionized. Ionization leads to depletion of the atomic density distribution observed by absorption imaging. The resonant ionization spectrum is reported. The setup used in this experiment is suitable not only to investigate mixtures of Bose-Einstein condensates and ions but also for single-atom detection on an atom chip.

  20. Double-photoionization of helium including quadrupole radiation effects

    SciTech Connect

    Colgan, James; Ludlow, J A; Lee, Teck - Ghee; Pindzola, M S; Robicheaux, F

    2009-01-01

    Non-perturbative time-dependent close-coupling calculations are carried out for the double photoionization of helium including both dipole and quadrupole radiation effects. At a photon energy of 800 eV, accessible at CUlTent synchrotron light sources, the quadrupole interaction contributes around 6% to the total integral double photoionization cross section. The pure quadrupole single energy differential cross section shows a local maxima at equal energy sharing, as opposed to the minimum found in the pure dipole single energy differential cross section. The sum of the pure dipole and pure quadrupole single energy differentials is insensitive to non-dipole effects at 800 eV. However, the triple differential cross section at equal energy sharing of the two ejected electrons shows strong non-dipole effects due to the quadrupole interaction that may be experimentally observable.

  1. Photoionization of Endohedral Atoms: Collective, Reflective and Collateral Emissions

    SciTech Connect

    Chakraborty, Himadri S.; McCune, Matthew A.; Hopper, Dale E.; Madjet, Mohamed E.; Manson, Steven T.

    2009-12-03

    The photoionization properties of a fullerene-confined atom differ dramatically from that of an isolated atom. In the low energy region, where the fullerene plasmons are active, the electrons of the confined atom emerge through a collective channel carrying a significant chunk of plasmon with it. The photoelectron angular distribution of the confined atom however shows far lesser impact of the effect. At higher energies, the interference between two single-electron ionization channels, one directly from the atom and another reflected off the fullerene cage, producuces oscillatory cross sections. But for the outermost atomic level, which transfers some electrons to the cage, oscillations are further modulated by the collateral emission from the part of the atomic charge density transferred to the cage. These various modes of emissions are studied for the photoionization of Ar endohedrally confined in C{sub 60}.

  2. Measuring Incorporation Of Arsenic In Molecular-Beam Expitaxy

    NASA Technical Reports Server (NTRS)

    Lewis, Blair F.; Fernandez, Rouel F.; Madhukar, Anupam; Grunthaner, Frank J.

    1988-01-01

    Changes in surface layers cause oscillations in RHEED measurements. Specular RHEED Beam intensity measured before, during, and after deposition of seven to eight monomolecular layers of gallium during 1.5 seconds. Arsenic pressure was 1.7x10 to the negative seventh power torr (2.3x10 to the negative fifth power Pa) throughout measurements.

  3. Measuring Incorporation Of Arsenic In Molecular-Beam Expitaxy

    NASA Technical Reports Server (NTRS)

    Lewis, Blair F.; Fernandez, Rouel F.; Madhukar, Anupam; Grunthaner, Frank J.

    1988-01-01

    Changes in surface layers cause oscillations in RHEED measurements. Specular RHEED Beam intensity measured before, during, and after deposition of seven to eight monomolecular layers of gallium during 1.5 seconds. Arsenic pressure was 1.7x10 to the negative seventh power torr (2.3x10 to the negative fifth power Pa) throughout measurements.

  4. Photoionization of hydroxymethyl (CD[sub 2]OH and CD[sub 2]OD) and methoxy (CD[sub 3]O) radicals. Photoion efficiency spectra, ionization energies, and thermochemistry

    SciTech Connect

    Kuo, S.C.; Zhang, Z.; Klemm, R.B. ); Liebman, J.F. ); Stief, L.J. ); Nesbitt, F.L. Coppin State College, Baltimore, MD )

    1994-04-14

    Photoion efficiency (PIE) spectra were obtained for CD[sub 2]OH, CD[sub 2]OD, and CD[sub 3]O radicals using the discharge flow-photoionization mass spectrometry technique. The radicals were generated in a flow tube via reaction of F atoms with the appropriate methanol isotopomers (CD[sub 3]OH [yields] CD[sub 2]OH, CD[sub 3]OD [yields] CD[sub 2]OD, and CD[sub 3]OH [yields] CD[sub 3]O), which were in large excess. Deuterated methoxy radicals, CD[sub 3]O, were also generated via the reaction of CD[sub 3] with NO[sub 2]. Photoionization of the radicals was achieved using high intensity, dispersed synchrotron radiation, and ionization energies (IE) of these radicals were derived from the thresholds of the PIE spectra: IE(CD[sub 2]OH) = 7.54 [+-] 0.02 eV, IE(CD[sub 2]OD) = 7.53 [+-] 0.02 eV, and IE(CD[sub 3]O) = 10.74 [+-] 0.02 eV. The PIE spectra for CD[sub 2]OH and CD[sub 3]O are compared to those of a previous photoionization study, and differences are discussed. Integration of previously published photoelectron spectroscopy data for CD[sub 2]OH yields a curve quite similar to our PIE spectrum. Empirical estimates of IE(CH[sub 2]OH) and IE(CH[sub 3]O) are given to corroborate our assignments. The measured ionization energies and the derived thermodynamic quantities are compared with previously reported results. 67 refs., 7 figs., 2 tabs.

  5. Dissociative double-photoionization of butadiene in the 25-45 eV energy range using 3-D multi-coincidence ion momentum imaging spectrometry

    SciTech Connect

    Oghbaie, Shabnam; Gisselbrecht, Mathieu; Laksman, Joakim; Månsson, Erik P.; Sankari, Anna; Sorensen, Stacey L.

    2015-09-21

    Dissociative double-photoionization of butadiene in the 25-45 eV energy range has been studied with tunable synchrotron radiation using full three-dimensional ion momentum imaging. Using ab initio calculations, the electronic states of the molecular dication below 33 eV are identified. The results of the measurement and calculation show that double ionization from π orbitals selectively triggers twisting about the terminal or central C–C bonds. We show that this conformational rearrangement depends upon the dication electronic state, which effectively acts as a gateway for the dissociation reaction pathway. For photon energies above 33 eV, three-body dissociation channels where neutral H-atom evaporation precedes C–C charge-separation in the dication species appear in the correlation map. The fragment angular distributions support a model where the dication species is initially aligned with the molecular backbone parallel to the polarization vector of the light, indicating a high probability for double-ionization to the “gateway states” for molecules with this orientation.

  6. Photoionization and electron-ion recombination of P II

    NASA Astrophysics Data System (ADS)

    Nahar, Sultana N.

    2017-08-01

    A study of the inverse processes of photoionization and electron-ion recombination of P ii is reported. Phosphorus, a little studied cosmic element, requires atomic parameters such as those presented here for spectral analysis. The unified method of Nahar and Pradhan, which incorporates two methods of recombination - radiative recombination (RR) and dielectronic recombination (DR) - and the interference between them, is used to obtain the total electron-ion recombination. This method implements the framework of the {R}-matrix close-coupling approximation. The present results include the partial photoionization cross-sections σPI(Jπ) leaving the residual ion in the ground level and level-specific recombination rate coefficients, αRC(Jπ), of 475 fine-structure levels of P ii with n ≤10. In photoionization of the ground and many excited levels, a sharp resonance is found to form at the ionization threshold from couplings of relativistic fine-structure channels. These, with other resonances in the near-threshold energy region, yield a slight curvature, in contrast to typical smooth decay, at a very low temperature of about 330 K in the total recombination rate coefficient αRC. The presence of other Rydberg and Seaton resonances in the photoionization cross-section introduces features in the level-specific recombination rate coefficients and a DR bump at high temperature at 105 K for the total recombination rate coefficient. Considerable interference between RR and DR is noted around 6700 K. The recombination spectrum with respect to photoelectron energy αRC(E) is also presented. The results are expected to provide accurate models for astrophysical plasmas up to ∼1 MK.

  7. Nonperturbative theory of double photoionization of the hydrogen molecule

    SciTech Connect

    Vanroose, W.; Martin, F.; Rescigno, T.N.; McCurdy, C.W.

    2004-10-01

    We present completely ab initio nonperturbative calculations of the integral and single differential cross sections for double photoionization of H2 for photon energies from 53.9 to 75.7 eV. The method of exterior complex scaling, implemented with B-splines, is used to solve the Schrodinger equation for a correlated continuum wave function corresponding to a single photon having been absorbed by a correlated initial state. The results are in good agreement with experimental integral cross sections.

  8. Tunable Wavelength Soft Photoionization of Ionic Liquid Vapors (Preprint)

    DTIC Science & Technology

    2009-11-18

    determined using the atomic absorption line spectrum of an argon gas filter located between the light Preprint Distribution A: Approved for public...Journal of the American Society for Mass Spectrometry; 19, 1347 (2008). 28. P.B. Corkum, Plasma Perspective on Strong-Field Multiphoton Ionization...Physical Review Letters; 71, 1994 (1993). 29. L. Belau et al., Vacuum ultraviolet ( VUV ) photoionization of small water clusters. Journal of

  9. Photoionization of an aluminum plasma by a tantalum X source

    NASA Astrophysics Data System (ADS)

    Renaudin, Patrick; Back, Christina A.; Chenais-Popovics, Claude; Audebert, Patrick; Geindre, Jean-Paul; Gauthier, Jean-Claude

    1991-05-01

    Photoionization of a helium like aliminum plasma is carried out by an external x-source. The laser beam used corresponds to the 3d to 4F transition level of tantalum. The experimental spectrum of tantalum is shown superimposed over the emission spectrum of aluminum on diagrammatic form. Good correspondence is seen between the 3d to 4F emissions of tantalum and helium like aluminum. Plasma pumping is obtained by exposure of a tantalum target to laser rays.

  10. Recent applications of synchrotron VUV photoionization mass spectrometry: insight into combustion chemistry.

    PubMed

    Li, Yuyang; Qi, Fei

    2010-01-19

    Combustion is one of the earliest developed human technologies and remains our primary source of energy, yet it embodies a complex suite of physical and chemical processes that are inadequately understood. Combustion chemistry involves both chemical thermodynamics and chemical kinetics, and experimental advances mostly depend on the development of combustion diagnostics, which effectively serve as the foundation of theoretical progress. The major objective of combustion diagnostics is to provide comprehensive product identification and concentration information of a flame species, which can be used to develop kinetic models for the simulation of practical combustion. However, conventional combustion diagnostic methods face difficult challenges in distinguishing isomeric species, detecting reactive radicals, obtaining real-time measurements, and so forth. Therefore, for deeper insight into combustion chemistry, a diagnostic method with high detection sensitivity, isomeric selectivity, and radical detectability is required. In this Account, we report recent applications of synchrotron vacuum ultraviolet photoionization mass spectrometry (SVUV-PIMS) in various areas of combustion chemistry research. The wide tunability of synchrotron photon energy can facilitate the selective identification of isomeric intermediates and the near-threshold detection of radicals (thus avoiding fragmentation interference). Moreover, the convenient combination of SVUV-PIMS with various laboratory-based combustion approaches demonstrates its universality in combustion studies. Recent experimental achievements have demonstrated the successful applications of this technique in premixed flames, pyrolysis in flow reactors, coflow diffusion flames, catalytic oxidation, plasma diagnostics, and analysis of polycyclic aromatic hydrocarbons (PAHs) and soot. More applications of SVUV-PIMS are expected in the near future, not only in combustion studies, but also in other research topics of chemistry

  11. Vibrationally Resolved B 1s Photoionization Cross Section of BF3.

    PubMed

    Ayuso, D; Kimura, M; Kooser, K; Patanen, M; Plésiat, E; Argenti, L; Mondal, S; Travnikova, O; Sakai, K; Palacios, A; Kukk, E; Decleva, P; Ueda, K; Martín, F; Miron, C

    2015-06-11

    Photoelectron diffraction is a well-established technique for structural characterization of solids, based on the interference of the native photoelectron wave with those scattered from the neighboring atoms. For isolated systems in the gas phase similar studies suffer from orders of magnitude lower signals due to the very small sample density. Here we present a detailed study of the vibrationally resolved B 1s photoionization cross section of BF3 molecule. A combination of high-resolution photoelectron spectroscopy measurements and of state-of-the-art static-exchange and time-dependent DFT calculations shows the evolution of the photon energy dependence of the cross section from a complete trapping of the photoelectron wave (low energies) to oscillations due to photoelectron diffraction phenomena. The diffraction pattern allows one to access structural information both for the ground neutral state of the molecule and for the core-ionized cation. Due to a significant change in geometry between the ground and the B 1s(-1) core-ionized state in the BF3 molecule, several vibrational final states of the cation are populated, allowing investigation of eight different relative vibrationally resolved photoionization cross sections. Effects due to recoil induced by the photoelectron emission are also discussed.

  12. Parametrizations and dynamical analysis of angle-integrated cross sections for double photoionization including nondipole effects

    SciTech Connect

    Istomin, Andrei Y.; Starace, Anthony F.; Manakov, N. L.; Meremianin, A. V.; Kheifets, A. S.; Bray, Igor

    2005-11-15

    Similarly to differential cross sections for one-electron photoionization, the doubly differential cross section for double photoionization (DPI) may be conveniently described by four parameters: the singly differential (with respect to energy sharing) cross section ({sigma}{sub 0}), the dipole asymmetry parameter ({beta}), and two nondipole asymmetry parameters ({gamma} and {delta}). Here we derive two model-independent representations for these parameters for DPI from a {sup 1}S{sub 0} atomic bound state: (i) in terms of one-dimensional integrals of the polarization-invariant DPI amplitudes and (ii) in terms of the exact two-electron reduced matrix elements. For DPI of He at excess energies, E{sub exc}, of 100 eV, 450 eV, and 1 keV, we present numerical results for the asymmetry parameters within the framework of the convergent close-coupling theory and compare them with results of lowest-order (in the interelectron interaction) perturbation theory (LOPT). The results for E{sub exc}=1 keV exhibit a nondipole asymmetry that is large enough to be easily measured experimentally. We find excellent agreement between our LOPT results and other theoretical predictions and experimental data for total cross sections and ratios of double to single ionization cross sections for K-shell DPI from several multielectron atoms.

  13. Photoionization of phenothiazine: EPR detection of reactions of the polarized solvated electron

    SciTech Connect

    Turro, N.J.; Khudyakov, I.V.; Willigen, H. van

    1995-12-13

    Photoionization of phenothiazine (PTH) and reactions of the solvated electron with some electron acceptors were studied with steady state and time-resolved EPR and transient optical absorption techniques. Time-resolved EPR spectra from the phenothiazine cation radical (PTH{sup .+}) and hydrated electron (e{sub aq}{sup -}) formed in sodium 1-dodecylsulfate (SDS) micellar solution were observed in emission. By contrast, PTH{sup .+} formed by photoionization of PTH in alcohols gives absorptive EPR signals. The spin polarization carried by the hydrated electron in SDS solutions can be transferred effectively to a stable nitroxyl free radical 3-carboxy-2,2,5, 5-tetramethyl-1-pyrrolidinyloxyl (N{sup .-}) present in the bulk aqueous phase. EPR and flash photolysis measurements show that this electron spin polarization transfer process proceeds with a rate which is approximately five times faster than the chemical reaction between e{sub aq}{sup -} and N{sup .-}. The marked difference in rates is attributed to differences in spin-statistical factors and difference in reaction radii for spin exchange compared to reaction. In alcohol solutions of PTH and a nitroxyl stable radical (2,2,6, 6-tetramethylpyperidin-1-oxyl, TEMPO), excitation of PTH also results in emissive polarization of the EPR spectrum of the stable radical. 46 refs., 12 figs.

  14. SOLAR PHOTOIONIZATION RATES FOR INTERSTELLAR NEUTRALS IN THE INNER HELIOSPHERE: H, He, O, AND Ne

    SciTech Connect

    Bochsler, P.; Kucharek, H.; Möbius, E.; Bzowski, Maciej; Sokół, Justyna M.; Didkovsky, Leonid; Wieman, Seth

    2014-01-01

    Extreme UV (EUV) spectra from the Thermosphere Ionosphere Mesosphere Energetics and Dynamics (TIMED)/Solar EUV Experiment are used to infer photoionization rates in the inner heliosphere. Relating these rates to various proxies describing the solar EUV radiation, we construct a multi-linear model which allows us to extrapolate ionization rates back to periods when no routine measurements of the solar EUV spectral distribution have been available. Such information is important, e.g., for comparing conditions of the interstellar neutral particles in the inner heliosphere at the time of Ulysses/GAS observations with conditions during the more recent observations of the Interstellar Boundary Explorer. From a period of 11 yr when detailed spectra from both TIMED and three proxies—Solar and Heliospheric Observatory/CELIAS/SEM-rates, F10.7 radio flux, and Mg II core-to-wing indices—have been available, we conclude that the simple model is able to reproduce the photoionization rates with an uncertainty of typically 5%.

  15. VUV photodynamics and chiral asymmetry in the photoionization of gas phase alanine enantiomers.

    PubMed

    Tia, Maurice; Cunha de Miranda, Barbara; Daly, Steven; Gaie-Levrel, François; Garcia, Gustavo A; Nahon, Laurent; Powis, Ivan

    2014-04-17

    The valence shell photoionization of the simplest proteinaceous chiral amino acid, alanine, is investigated over the vacuum ultraviolet region from its ionization threshold up to 18 eV. Tunable and variable polarization synchrotron radiation was coupled to a double imaging photoelectron/photoion coincidence (i(2)PEPICO) spectrometer to produce mass-selected threshold photoelectron spectra and derive the state-selected fragmentation channels. The photoelectron circular dichroism (PECD), an orbital-sensitive, conformer-dependent chiroptical effect, was also recorded at various photon energies and compared to continuum multiple scattering calculations. Two complementary vaporization methods-aerosol thermodesorption and a resistively heated sample oven coupled to an adiabatic expansion-were applied to promote pure enantiomers of alanine into the gas phase, yielding neutral alanine with different internal energy distributions. A comparison of the photoelectron spectroscopy, fragmentation, and dichroism measured for each of the vaporization methods was rationalized in terms of internal energy and conformer populations and supported by theoretical calculations. The analytical potential of the so-called PECD-PICO detection technique-where the electron spectroscopy and circular dichroism can be obtained as a function of mass and ion translational energy-is underlined and applied to characterize the origin of the various species found in the experimental mass spectra. Finally, the PECD findings are discussed within an astrochemical context, and possible implications regarding the origin of biomolecular asymmetry are identified.

  16. Vibrationally specific photoionization cross sections of acrolein leading to the X̃²A' ionic state.

    PubMed

    López-Domínguez, Jesús A; Lucchese, Robert R; Fulfer, K D; Hardy, David; Poliakoff, E D; Aguilar, A A

    2014-09-07

    The vibrational branching ratios in the photoionization of acrolein for ionization leading to the X̃²A' ion state were studied. Computed logarithmic derivatives of the cross section and the corresponding experimental data derived from measured vibrational branching ratios for several normal modes (ν9, ν10, ν11, and ν12) were found to be in relatively good agreement, particularly for the lower half of the 11-100 eV photon energy range considered. Two shape resonances have been found near photon energies of 15.5 and 23 eV in the photoionization cross section and have been demonstrated to originate from the partial cross section of the A' scattering symmetry. The wave functions computed at the resonance complex energies are delocalized over the whole molecule. By looking at the dependence of the cross section on the different normal mode displacements together with the wave function at the resonant energy, a qualitative explanation is given for the change of the cross sections with respect to changing geometry.

  17. Photoionization Modeling and the K Lines of Iron

    NASA Technical Reports Server (NTRS)

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

    2004-01-01

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

  18. Solvent jet desorption capillary photoionization-mass spectrometry.

    PubMed

    Haapala, Markus; Teppo, Jaakko; Ollikainen, Elisa; Kiiski, Iiro; Vaikkinen, Anu; Kauppila, Tiina J; Kostiainen, Risto

    2015-03-17

    A new ambient mass spectrometry method, solvent jet desorption capillary photoionization (DCPI), is described. The method uses a solvent jet generated by a coaxial nebulizer operated at ambient conditions with nitrogen as nebulizer gas. The solvent jet is directed onto a sample surface, from which analytes are extracted into the solvent and ejected from the surface in secondary droplets formed in collisions between the jet and the sample surface. The secondary droplets are directed into the heated capillary photoionization (CPI) device, where the droplets are vaporized and the gaseous analytes are ionized by 10 eV photons generated by a vacuum ultraviolet (VUV) krypton discharge lamp. As the CPI device is directly connected to the extended capillary inlet of the MS, high ion transfer efficiency to the vacuum of MS is achieved. The solvent jet DCPI provides several advantages: high sensitivity for nonpolar and polar compounds with limit of detection down to low fmol levels, capability of analyzing small and large molecules, and good spatial resolution (250 μm). Two ionization mechanisms are involved in DCPI: atmospheric pressure photoionization, capable of ionizing polar and nonpolar compounds, and solvent assisted inlet ionization capable of ionizing larger molecules like peptides. The feasibility of DCPI was successfully tested in the analysis of polar and nonpolar compounds in sage leaves and chili pepper.

  19. Covariation Is a Poor Measure of Molecular Coevolution.

    PubMed

    Talavera, David; Lovell, Simon C; Whelan, Simon

    2015-09-01

    Recent developments in the analysis of amino acid covariation are leading to breakthroughs in protein structure prediction, protein design, and prediction of the interactome. It is assumed that observed patterns of covariation are caused by molecular coevolution, where substitutions at one site affect the evolutionary forces acting at neighboring sites. Our theoretical and empirical results cast doubt on this assumption. We demonstrate that the strongest coevolutionary signal is a decrease in evolutionary rate and that unfeasibly long times are required to produce coordinated substitutions. We find that covarying substitutions are mostly found on different branches of the phylogenetic tree, indicating that they are independent events that may or may not be attributable to coevolution. These observations undermine the hypothesis that molecular coevolution is the primary cause of the covariation signal. In contrast, we find that the pairs of residues with the strongest covariation signal tend to have low evolutionary rates, and that it is this low rate that gives rise to the covariation signal. Slowly evolving residue pairs are disproportionately located in the protein's core, which explains covariation methods' ability to detect pairs of residues that are close in three dimensions. These observations lead us to propose the "coevolution paradox": The strength of coevolution required to cause coordinated changes means the evolutionary rate is so low that such changes are highly unlikely to occur. As modern covariation methods may lead to breakthroughs in structural genomics, it is critical to recognize their biases and limitations. © The Author 2015. Published by Oxford University Press on behalf of the Society for Molecular Biology and Evolution.

  20. Picosecond time resolved conductance measurements of redox molecular junctions

    NASA Astrophysics Data System (ADS)

    Arielly, Rani; Nachman, Nirit; Zelinskyy, Yaroslav; May, Volkhard; Selzer, Yoram

    2017-03-01

    Due to bandwidth limitations of state of the art electronics, the transient transport properties of molecular junctions are experimentally a terra incognita, which can only be explored if novel picosecond current-probing techniques are developed. Here we demonstrate one such approach: the laser pulse-pair sequence scheme. The method is used to monitor in picosecond resolution the oxidation state of a redox molecule, 6-ferrocenyl-1-hexanethiol, within a junction and to quantify its redox rate constant, which is found to be (80 ps)-1.

  1. Molecular Emission and Temperature Measurements from Single-Bubble Sonoluminescence

    NASA Astrophysics Data System (ADS)

    Xu, Hangxun; Suslick, Kenneth S.

    2010-06-01

    Single-bubble sonoluminescence (SBSL) spectra in H2O show featureless continuum emission. From an acoustically driven, moving bubble in phosphoric acid (H3PO4), we observe very strong molecular emission from excited OH radicals (˜310nm), which can be used as a spectroscopic thermometer by fitting the experimental SBSL spectra to the OH AΣ+2-XΠ2 rovibronic transitions. The observed emission temperature (Tem) ranges from 6200 to 9500 K as the acoustic pressure (Pa) varies from 1.9 to 3.1 bar and from 6000 to >10000K as the dissolved monatomic gas varies over the series from He to Xe.

  2. Femtosecond pump-probe photoionization-photofragmentation spectroscopy: Photoionization-induced twisting and coherent vibrational motion of azobenzene cation

    NASA Astrophysics Data System (ADS)

    Ho-Wei, Jr.; Chen, Wei-Kan; Cheng, Po-Yuan

    2009-10-01

    We report studies of ultrafast dynamics of azobenzene cation using femtosecond photoionization-photofragmentation spectroscopy. In our experiments, a femtosecond pump pulse first produces an ensemble of azobenzene cations via photoionization of the neutrals. A delayed probe pulse then brings the evolving ionic system to excited states that ultimately undergo ion fragmentation. The dynamics is followed by monitoring either the parent-ion depletion or fragment-ion formation as a function of the pump-probe delay time. The observed transients for azobenzene cation are characterized by a constant ion depletion modulated by a rapidly damped oscillatory signal with a period of about 1 ps. Theoretical calculations suggest that the oscillation arises from a vibration motion along the twisting inversion coordinate involving displacements in CNNC and phenyl-ring torsions. The oscillation is damped rapidly with a time constant of about 1.2 ps, suggesting that energy dissipation from the active mode to bath modes takes place in this time scale.

  3. Covariation Is a Poor Measure of Molecular Coevolution

    PubMed Central

    Talavera, David; Lovell, Simon C.; Whelan, Simon

    2015-01-01

    Recent developments in the analysis of amino acid covariation are leading to breakthroughs in protein structure prediction, protein design, and prediction of the interactome. It is assumed that observed patterns of covariation are caused by molecular coevolution, where substitutions at one site affect the evolutionary forces acting at neighboring sites. Our theoretical and empirical results cast doubt on this assumption. We demonstrate that the strongest coevolutionary signal is a decrease in evolutionary rate and that unfeasibly long times are required to produce coordinated substitutions. We find that covarying substitutions are mostly found on different branches of the phylogenetic tree, indicating that they are independent events that may or may not be attributable to coevolution. These observations undermine the hypothesis that molecular coevolution is the primary cause of the covariation signal. In contrast, we find that the pairs of residues with the strongest covariation signal tend to have low evolutionary rates, and that it is this low rate that gives rise to the covariation signal. Slowly evolving residue pairs are disproportionately located in the protein’s core, which explains covariation methods’ ability to detect pairs of residues that are close in three dimensions. These observations lead us to propose the “coevolution paradox”: The strength of coevolution required to cause coordinated changes means the evolutionary rate is so low that such changes are highly unlikely to occur. As modern covariation methods may lead to breakthroughs in structural genomics, it is critical to recognize their biases and limitations. PMID:25944916

  4. Near-threshold photoelectron angular distributions from two-photon resonant photoionization of He

    NASA Astrophysics Data System (ADS)

    O'Keeffe, P.; Mihelič, A.; Bolognesi, P.; Žitnik, M.; Moise, A.; Richter, R.; Avaldi, L.

    2013-01-01

    Two-photon resonant photoionization of helium is investigated both experimentally and theoretically. Ground state helium atoms are excited to the 1s4p, 1s5p and 1s6p 1P states by synchrotron radiation and ionized by a synchronized infrared pulsed picosecond laser. The photoelectron angular distributions of the emitted electrons are measured using a velocity map imaging (VMI) spectrometer. The measured asymmetry parameters of the angular distribution allow the phase differences and the ratios of the dipole matrix elements of the 1sɛs and 1sɛd channels to be determined. The experimental results agree with the calculated values obtained in a configuration-interaction calculation with a Coulomb-Sturmian basis set. The effects of the radiative decay of the intermediate state and the static electric field of the VMI spectrometer on the measurements are discussed.

  5. Molecular-scale measurements of electric fields at electrochemical interfaces.

    SciTech Connect

    Hayden, Carl C.; Farrow, Roger L.

    2011-01-01

    Spatially resolved measurements of electric fields at electrochemical interfaces would be a critical step toward further understanding and modeling the detailed structure of electric double layers. The goal of this project was to perform proof-of-principle experiments to demonstrate the use of field-sensitive dyes for optical measurements of fields in electrochemical systems. A confocal microscope was developed that provides sensitive detection of the lifetime and high resolution spectra of excited fluorescence for dyes tethered to electrically conductive surfaces. Excited state lifetimes for the dyes were measured and found to be relatively unquenched when linked to indium tin oxide, but strongly quenched on gold surfaces. However, our fluorescence detection is sufficiently sensitive to measure spectra of submonolayer dye coatings even when the fluorescence was strongly quenched. Further work to create dye labeled interfaces on flat, uniform and durable substrates is necessary to make electric field measurements at interfaces using field sensitive dyes.

  6. Tunable far infrared studies of molecular parameters in support of stratospheric measurements

    NASA Technical Reports Server (NTRS)

    Chance, K. V.; Nolt, Ira G.; Radostitz, J. V.; Park, K.

    1990-01-01

    The purpose of this research is to make precise, fully line-resolved measurements of molecular parameters that are necessary for the analysis of spectra obtained in far infrared field measurement programs. These measurements make it possible to accurately analyze the data from field measurements to obtain atmospheric concentration profiles of key trace gases involved in the ozone chemistry. The research objectives include: measurements of pressure broadening of molecular lines of OH, O2, O3, HCl, and H2O, their temperature dependence, and, when possible, the pressure-induced frequency shifts of the lines; measurements of line positions of radical species, such as HO2.

  7. Photoionized Plasmas in the Z Facility and in Astrophysics

    NASA Astrophysics Data System (ADS)

    Mancini, Roberto

    2013-06-01

    Many astrophysical environments such as x-ray binaries, active galactic nuclei, and accretion disks of compact objects have photoionized plasmas. Detailed x-ray spectral observations performed with the Chandra and XMM-Newton orbiting telescopes provide critical information on the state of photoionized plasmas. However, the complexity of the astrophysical environment makes the spectral analysis challenging, and thus laboratory experiments are important for data interpretation and testing of modeling codes. The Z facility at Sandia National Laboratories is a powerful source of x-rays to produce and study in the laboratory photoionized plasmas relevant for astrophysics under well characterized conditions. We discuss an experimental and theory/modeling effort in which the intense x-ray flux emitted at the collapse of a z-pinch implosion conducted at the Z pulsed-power machine is employed to produce a neon photoionized plasma. The broadband x-ray radiation flux from the z-pinch is used to both create the photoionized plasma and provide a source of backlighting photons to study the atomic kinetics through K-shell line absorption spectroscopy. The plasma is contained in a cm-scale gas cell that can be located at different distances from the z-pinch, thus effectively controlling the x-ray flux producing the plasma. Time-integrated and gated transmission spectra are recorded with a spectrometer equipped with two elliptically-bent KAP crystals and a set of slits to record up to six spatially-resolved spectra per crystal in the same shot. The transmission data shows a rich line absorption spectrum that spans over several ionization stages of neon including Be-, Li-, He- and H-like ions. Modeling calculations are used to interpret the transmission spectra recorded in the Z experiments with the goal of extracting the charge- state distribution, electron temperature and the radiation flux driving the plasma, as well as to determine the ionization parameter of the plasma. This

  8. The measurement of molecular diversity: A three-dimensional approach

    NASA Astrophysics Data System (ADS)

    Chapman, David

    1996-12-01

    This paper describes a method for selecting a small, highly diverse subset from a large pool of molecules. The method has been employed in the design of combinatorial synthetic libraries for use in high-throughput screening for pharmaceutical lead generation. It computes diversity in terms of the main factors relevant to ligand-protein binding, namely the three-dimensional arrangement of steric bulk and of polar functionalities and molecular entropy. The method was used to select a set of 20 carboxylates suitable for use as side-chain precursors in a polyamine-based library. The method depends on estimates of various physical-chemical parameters involved in ligand-protein binding; experiments examined the sensitivity of the method to these parameters. This paper compares the diversity of randomly and rationally selected side-chain sets; the results suggest that careful design of synthetic combinatorial libraries may increase their effectiveness several-fold.

  9. Molecular emission and temperature measurements from single-bubble sonoluminescence.

    PubMed

    Xu, Hangxun; Suslick, Kenneth S

    2010-06-18

    Single-bubble sonoluminescence (SBSL) spectra in H2O show featureless continuum emission. From an acoustically driven, moving bubble in phosphoric acid (H3PO4), we observe very strong molecular emission from excited OH radicals (∼310  nm), which can be used as a spectroscopic thermometer by fitting the experimental SBSL spectra to the OH A 2Σ+ - X 2Π rovibronic transitions. The observed emission temperature (T(em)) ranges from 6200 to 9500 K as the acoustic pressure (P(a)) varies from 1.9 to 3.1 bar and from 6000 to >10,000  K as the dissolved monatomic gas varies over the series from He to Xe.

  10. Molecular methods to measure intestinal bacteria: a review.

    PubMed

    Inglis, G Douglas; Thomas, Matthew C; Thomas, Dallas K; Kalmokoff, Martin L; Brooks, Stephen P J; Selinger, L Brent

    2012-01-01

    The intestine is an exceptionally rich ecosystem encompassing a complex interaction among microorganisms, influenced by host factors, ingested food, and liquid. Characterizing the intestinal microbiota is currently an active area of research. Various molecular-based methods are available to characterize the intestinal microbiota, but all methods possess relative strengths, as well as salient weaknesses. It is important that researchers are cognizant of the limitations of these methods, and that they take the appropriate steps to mitigate weaknesses. Here, we discuss methodologies used to monitor intestinal bacteria including: (i) traditional clone libraries; (ii) direct sequencing using next-generation parallel sequencing technology; (iii) denaturing gradient gel electrophoresis and temperature gradient gel electrophoresis; (iv) terminal restriction fragment length polymorphism analysis; (v) fluorescent in situ hybridization; and (vi) quantitative PCR. In addition, we also discuss experimental design, sample collection and storage, DNA extraction, gene targets, PCR bias, and methods to reduce PCR bias.

  11. Can dynamic contact angle be measured using molecular modeling?

    PubMed

    Malani, Ateeque; Raghavanpillai, Anilkumar; Wysong, Ernest B; Rutledge, Gregory C

    2012-11-02

    A method is presented for determining the dynamic contact angle at the three-phase contact between a solid, a liquid, and a vapor under an applied force, using molecular simulation. The method is demonstrated using a Lennard-Jones fluid in contact with a cylindrical shell of the fcc Lennard-Jones solid. Advancing and receding contact angles and the contact angle hysteresis are reported for the first time by this approach. The increase in force required to wet fully an array of solid cylinders (robustness) with decreasing separation distance between cylinders is evaluated. The dynamic contact angle is characterized by partial slipping of the three phase contact line when a force is applied.

  12. Site-specific recoil-induced effects on inner-shell photoionization of linear triatomic molecules: N 1 s photoelectron spectra of N2 O

    NASA Astrophysics Data System (ADS)

    Krivosenko, Yu. S.; Pavlychev, A. A.

    2016-11-01

    We investigate hard X-ray ionization of linear triatomic molecules accenting recoil-induced effects on the dynamics of molecular frame. This dynamics is studied within the two-springs and harmonic approximations. The mode-channel relationship connecting the excitations of vibrational, rotational and translational degrees of freedom with the Σ → Σ and Σ → Π photoionization channels is applied to compute the N 1s-1 photoelectron spectra of molecular N2 O for various photon energies. The distinct ionized-site- and molecular-orientation-specific changes in the vibration structure of the 1 s photoelectron lines of terminal and central nitrogen atoms are revealed and discussed.

  13. Ultrafast Molecular Dynamics probed by Vacuum Ultraviolet Pulses

    NASA Astrophysics Data System (ADS)

    Cryan, James; Champenois, Elio; Shivaram, Niranjan; Wright, Travis; Yang, Chan-Shan; Falcone, Roger; Belkacem, Ali

    2014-05-01

    We present time-resolved measurements of the relaxation dynamics in small molecular systems (CO2 and C2H4) following ultraviolet (UV) photo-excitation. We probe these excitations through photoionization and velocity map imaging (VMI) spectroscopy. Vacuum and extreme ultraviolet (VUV/XUV) pump and probe pulses are created by exploiting strong-field high harmonic generation (HHG) from our state-of-the-art 30 mJ, 1 kHz laser system. Three dimensional photoelectron and photoion momentum images recorded with our VMI spectrometer reveal non-Born Oppenheimer dynamics in the vicinity of a conical intersection, and allow us track the state of the system as a function of time. We also present initial experiments with the goal of controlling the dynamics near a conical intersection using a strong-field IR pulse. Finally, we will show progress towards measurements of time-resolved molecular frame photoelectron angular distributions (TRMFPADs) by applying our VUV/XUV pulse sequence to an aligned molecular ensemble. Supported by Chemical Sciences, Geosciences and Biosciences division of BES/DOE.

  14. Measuring Molecular Forces Using Calibrated Optical Tweezers in Living Cells

    PubMed Central

    Hendricks, Adam G.; Goldman, Yale E.

    2017-01-01

    Optical tweezers have been instrumental in uncovering the mechanisms motor proteins use to generate and react to force. While optical traps have primarily been applied to purified, in vitro systems, emerging methods enable measurements in living cells where the actively fluctuating, viscoelastic environment and varying refractive index complicate calibration of the instrument. Here, we describe techniques to calibrate optical traps in living cells using the forced response to sinusoidal oscillations and spontaneous fluctuations, and to measure the forces exerted by endogenous ensembles of kinesin and dynein motor proteins as they transport cargoes in the cell. PMID:27844443

  15. Measuring Molecular Forces Using Calibrated Optical Tweezers in Living Cells.

    PubMed

    Hendricks, Adam G; Goldman, Yale E

    2017-01-01

    Optical tweezers have been instrumental in uncovering the mechanisms motor proteins use to generate and react to force. While optical traps have primarily been applied to purified, in vitro systems, emerging methods enable measurements in living cells where the actively fluctuating, viscoelastic environment and varying refractive index complicate calibration of the instrument. Here, we describe techniques to calibrate optical traps in living cells using the forced response to sinusoidal oscillations and spontaneous fluctuations, and to measure the forces exerted by endogenous ensembles of kinesin and dynein motor proteins as they transport cargoes in the cell.

  16. Chromatographic molecular weight measurements for heparin, its fragments and fractions, and other glycosaminoglycans.

    PubMed

    Mulloy, Barbara; Hogwood, John

    2015-01-01

    Glycosaminoglycan samples are usually polydisperse, consisting of molecules with differing length and differing sequence. Methods for measuring the molecular weight of heparin have been developed to assure the quality and consistency of heparin products for medicinal use, and these methods can be applied in other laboratory contexts. In the method described here, high-performance gel permeation chromatography is calibrated using appropriate heparin molecular weight markers or a single broad standard calibrant, and used to characterize the molecular weight distribution of polydisperse samples or the peak molecular weight of monodisperse, or approximately monodisperse, heparin fractions. The same technology can be adapted for use with other glycosaminoglycans.

  17. A combined electron-ion spectrometer for studying complete kinematics of molecular dissociation upon shell selective ionization

    SciTech Connect

    Saha, K.; Banerjee, S. B.; Bapat, B.

    2013-07-15

    A combined electron-ion spectrometer has been built to study dissociation kinematics of molecular ions upon various electronic decay processes ensuing from ionization of neutral molecules. The apparatus can be used with various ionization agents. Ion time-of-flight (ToF) spectra arising from various electronic decay processes are acquired by triggering the ToF measurement in coincidence with energy analyzed electrons. The design and the performance of the spectrometer in a photoionization experiment is presented in detail. Electron spectra and ion time of flight spectra resulting from valence and 2p{sub 1/2} ionization of Argon and those from valence ionization of CO are presented to demonstrate the capability of the instrument. The fragment ion spectra show remarkable differences (both kinematic and cross sectional) dependent on the energy of the ejected electron, corresponding to various electron loss and decay mechanisms in dissociative photoionization of molecules.

  18. Magnetic Field Structure in Molecular Clouds by Polarization Measurements

    NASA Astrophysics Data System (ADS)

    Chen, W. P.; Su, B. H.; Eswaraiah, C.; Pandey, A. K.; Wang, C. W.; Lai, S. P.; Tamura, M.; Sato, S.

    2015-03-01

    We report on a program to delineate magnetic field structure inside molecular clouds by optical and infrared polarization observations. An ordered magnetic field inside a dense cloud may efficiently align the spinning dust grains to cause a detectable level of optical and near-infrared polarization of otherwise unpolarized background starlight due to dichroic extinction. The near-infrared polarization data were taken by SIRPOL mounted on IRSF in SAAO. Here we present the SIRPOL results in RCW 57, for which the magnetic field is oriented along the cloud filaments, and in Carina Nebula, for which no intrinsic polarization is detected in the turbulent environment. We further describe TRIPOL, a compact and efficient polarimer to acquire polarized images simultaneously at g', r', and i' bands, which is recently developed at Nagoya University for adaption to small-aperture telescopes. We show how optical observations probe the translucent outer parts of a cloud, and when combining with infrared observations probing the dense parts, and with millimeter and submillimeter observations to sutdy the central embedded protostar, if there is one, would yield the magnetic field structure on different length scales in the star-formation process.

  19. Percent-level accuracy in measuring photoionisation yields and peak intensities for intense few-cycle laser pulses

    NASA Astrophysics Data System (ADS)

    Kielpinski, David; Wallace, W. C.; Ghafur, O.; Calvert, J. E.; Khurmi, C.; Laban, D. E.; Litvinyuk, I. V.; Sang, R. T.; Bartschat, K.; Grum-Grzhimailo, A. N.; Wells, D.; Quiney, H. M.; Tong, X. M.

    2014-05-01

    The correct interpretation of experimental results in strong-field physics depends critically on both the measurement precision and on accurate knowledge of the laser peak intensity. We have accurately measured the photoionization yields of atomic hydrogen (H) and molecular hydrogen (H2) in intense, few-cycle laser pulses, and compared them against various theoretical models. From our comparison with highly precise numerical solutions of the three-dimensional (3D) time-dependent Schrödinger equation (TDSE), we have derived an intensity calibration standard accurate to better than 3%. This standard is easily usable in any strong-field physics experiment capable of measuring photoionization yields. Supported by AFOSR and the Australian Research Council.

  20. Time-reversal Studies in Photorecombination and Photoionization Experiments with Ion Beams

    NASA Astrophysics Data System (ADS)

    Müller, A.; Schippers, S.; Aguilar, A.; Alvarez, I.; Bannister, M. E.; Bozek, J.; Cisneros, C.; Covington, A. M.; Dunn, G. H.; Gharaibeh, M. F.; Hinojosa, G.; Ricz, S.; Schlachter, A. S.; Phaneuf, R. A.

    2003-08-01

    The principle of detailed balance relates the cross sections σPR for photorecombination (PR) and σPI for photoionization (PI) of ions on a state-to-state level. Measuring one or the other of the two cross sections provides direct information about the time-reversed process. Measurements carried out at the Advanced Light Source, Berkeley, for PI of C2+ and Sc2+ are compared with experimental results from the heavy-ion storage ring TSR, Heidelberg, on PR of C3+ and Sc3+, respectively. From that comparison, state selective cross sections can be inferred both for PR and PI. Both experimental approaches provide possibilities for high-resolution spectroscopy of multiply excited states.