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Sample records for photoelectron photoion coincidence

  1. Imaging photoelectron photoion coincidence spectroscopy with velocity focusing electron optics

    SciTech Connect

    Bodi, Andras; Johnson, Melanie; Gerber, Thomas; Gengeliczki, Zsolt; Sztaray, Balint; Baer, Tomas

    2009-03-15

    An imaging photoelectron photoion coincidence spectrometer at the vacuum ultraviolet (VUV) beamline of the Swiss Light Source is presented and a few initial measurements are reported. Monochromatic synchrotron VUV radiation ionizes the cooled or thermal gas-phase sample. Photoelectrons are velocity focused, with better than 1 meV resolution for threshold electrons, and also act as start signal for the ion time-of-flight analysis. The ions are accelerated in a relatively low, 40-80 V cm{sup -1} field, which enables the direct measurement of rate constants in the 10{sup 3}-10{sup 7} s{sup -1} range. All electron and ion events are recorded in a triggerless multiple-start/multiple-stop setup, which makes it possible to carry out coincidence experiments at >100 kHz event frequencies. As examples, the threshold photoelectron spectrum of the argon dimer and the breakdown diagrams for hydrogen atom loss in room temperature methane and the chlorine atom loss in cold chlorobenzene are shown and discussed.

  2. Photoion-photoelectron coincidence studies clusters and transient molecules

    SciTech Connect

    Norwood, K.

    1990-11-16

    Experimental photoion-photoelectron coincidence (PIPECO) spectra have been obtained at different nozzle stagnation pressures for Ar, Kr, Xe, and CO dimers and trimers in the wavelength regions corresponding to the respective ground states through all states accessible with a photon energy of 20 eV. Ionization energies for all ground states were measured and agree well with previously reported values. The formation of stable dimer ions from fragmentation of larger cluster ions initially produced by photoionization is efficient. For nozzle expansion conditions which minimize the formation of clusters larger than dimers, the intensities of the excited PIPECO bands for all clusters, except Ar{sub 2}{sup +} and Ar{sub 3}{sup +}, are found to be negligible with respect to the ground state PIPECO bands. The PIPECO technique has been used successfully to obtain the mass-selected threshold photoelectron spectra of the SO and S{sub 2}O transient molecules formed from a microwave discharge, effusive beam source. Analysis of the PIPECO spectra of all the clusters and transient molecules are presented. 177 refs., 32 figs., 6 tabs.

  3. Velocity map photoelectron-photoion coincidence imaging on a single detector

    SciTech Connect

    Lehmann, C. Stefan; Ram, N. Bhargava; Janssen, Maurice H. M.

    2012-09-15

    Here we report on a new simplified setup for velocity map photoelectron-photoion coincidence imaging using only a single particle detector. We show that both photoelectrons and photoions can be extracted toward the same micro-channel-plate delay line detector by fast switching of the high voltages on the ion optics. This single detector setup retains essentially all the features of a standard two-detector coincidence imaging setup, viz., the high spatial resolution for electron and ion imaging, while only slightly decreasing the ion time-of-flight mass resolution. The new setup paves the way to a significant cost reduction in building a coincidence imaging setup for experiments aiming to obtain the complete correlated three-dimensional momentum distribution of electrons and ions.

  4. Disentangling Multichannel Photodissociation Dynamics in Acetone by Time-Resolved Photoelectron-Photoion Coincidence Spectroscopy.

    PubMed

    Maierhofer, Paul; Bainschab, Markus; Thaler, Bernhard; Heim, Pascal; Ernst, Wolfgang E; Koch, Markus

    2016-08-18

    For the investigation of photoinduced dynamics in molecules with time-resolved pump-probe photoionization spectroscopy, it is essential to obtain unequivocal information about the fragmentation behavior induced by the laser pulses. We present time-resolved photoelectron-photoion coincidence (PEPICO) experiments to investigate the excited-state dynamics of isolated acetone molecules triggered by two-photon (269 nm) excitation. In the complex situation of different relaxation pathways, we unambiguously identify three distinct pump-probe ionization channels. The high selectivity of PEPICO detection allows us to observe the fragmentation behavior and to follow the time evolution of each channel separately. For channels leading to fragment ions, we quantitatively obtain the fragment-to-parent branching ratio and are able to determine experimentally whether dissociation occurs in the neutral molecule or in the parent ion. These results highlight the importance of coincidence detection for the interpretation of time-resolved photochemical relaxation and dissociation studies if multiple pathways are present. PMID:27459051

  5. In situ flame chemistry tracing by imaging photoelectron photoion coincidence spectroscopy

    SciTech Connect

    Oßwald, P.; Köhler, M.; Hemberger, P.; Bodi, A.; Gerber, T.; Bierkandt, T.; Akyildiz, E.; Kasper, T.

    2014-02-15

    Adaptation of a low-pressure flat flame burner with a flame-sampling interface to the imaging photoelectron photoion coincidence spectrometer (iPEPICO) of the VUV beamline at the Swiss Light Source is presented. The combination of molecular-beam mass spectrometry and iPEPICO provides a new powerful analytical tool for the detailed investigation of reaction networks in flames. First results demonstrate the applicability of the new instrument to comprehensive flame diagnostics and the potentially high impact for reaction mechanism development for conventional and alternative fuels. Isomer specific identification of stable and radical flame species is demonstrated with unrivaled precision. Radical detection and identification is achieved for the initial H-abstraction products of fuel molecules as well as for the reaction controlling H, O, and OH radicals. Furthermore, quantitative evaluation of changing species concentrations during the combustion process and the applicability of respective results for kinetic model validation are demonstrated. Utilization of mass-selected threshold photoelectron spectra is shown to ensure precise signal assignment and highly reliable spatial profiles.

  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. Double imaging photoelectron photoion coincidence sheds new light on the dissociation of energy-selected CH3Cl(+) ions.

    PubMed

    Tang, Xiaofeng; Lin, Xiaoxiao; Zhang, Weijun; Garcia, Gustavo A; Nahon, Laurent

    2016-09-14

    The vacuum ultraviolet (VUV) photoionization and dissociative photoionization of CH3Cl in the energy range of 11-17 eV have been investigated in detail by combining synchrotron radiation and double imaging photoelectron photoion coincidences (i(2)PEPICO). Three low-lying electronic states of the CH3Cl(+) molecular ion, X(2)E, A(2)A1 and B(2)E, were prepared and analyzed. The appearance energies of the energetically accessible fragment ions, CH2Cl(+), CHCl(+), CH3(+) and CH2(+), have been obtained from their respective mass-selected threshold photoelectron spectra (TPES) or photoionization efficiency (PIE) curves. The dissociation mechanisms of energy-selected CH3Cl(+) ions, prepared in the A(2)A1 and the B(2)E electronic states, as well as outside the Franck-Condon region, have been revealed to be state-specific via ion/electron kinetic energy correlation diagrams. In particular, the umbrella mode vibrational progression of the CH3(+) fragment ion in the direct dissociation of the A(2)A1 electronic state was identified and assigned indicating that this state correlates to the CH3(+)(1(1)A1') + Cl((2)P1/2) dissociation limit, in agreement with the theoretical calculations performed in this work. PMID:27524637

  8. Synchrotron-based double imaging photoelectron/photoion coincidence spectroscopy of radicals produced in a flow tube: OH and OD

    NASA Astrophysics Data System (ADS)

    Garcia, Gustavo A.; Tang, Xiaofeng; Gil, Jean-François; Nahon, Laurent; Ward, Michael; Batut, Sebastien; Fittschen, Christa; Taatjes, Craig A.; Osborn, David L.; Loison, Jean-Christophe

    2015-04-01

    We present a microwave discharge flow tube coupled with a double imaging electron/ion coincidence device and vacuum ultraviolet (VUV) synchrotron radiation. The system has been applied to the study of the photoelectron spectroscopy of the well-known radicals OH and OD. The coincidence imaging scheme provides a high selectivity and yields the spectra of the pure radicals, removing the ever-present contributions from excess reactants, background, or secondary products, and therefore obviating the need for a prior knowledge of all possible byproducts. The photoelectron spectra encompassing the X3Σ- ground state of the OH+ and OD+ cations have been extracted and the vibrational constants compared satisfactorily to existing literature values. Future advantages of this approach include measurement of high resolution VUV spectroscopy of radicals, their absolute photoionization cross section, and species/isomer identification in chemical reactions as a function of time.

  9. Synchrotron-based double imaging photoelectron/photoion coincidence spectroscopy of radicals produced in a flow tube: OH and OD

    DOE PAGESBeta

    Garcia, Gustavo A.; Tang, Xiaofeng; Gil, Jean -Francois; Nahon, Laurent; Ward, Michael; Batut, Sebastien; Fittschen, Christa; Taatjes, Craig A.; Osborn, David L.; Loison, Jean -Christophe

    2015-04-23

    In this study, we present a microwave discharge flow tube coupled with a double imaging electron/ion coincidence device and vacuum ultraviolet (VUV) synchrotron radiation. The system has been applied to the study of the photoelectron spectroscopy of the well-known radicals OH and OD. The coincidence imaging scheme provides a high selectivity and yields the spectra of the pure radicals, removing the ever-present contributions from excess reactants, background, or secondary products, and therefore obviating the need for a prior knowledge of all possible byproducts. The photoelectron spectra encompassing the X3Σ– ground state of the OH+ and OD+ cations have been extractedmore » and the vibrational constants compared satisfactorily to existing literature values. Future advantages of this approach include measurement of high resolution VUV spectroscopy of radicals, their absolute photoionization cross section, and species/isomer identification in chemical reactions as a function of time.« less

  10. Synchrotron-based double imaging photoelectron/photoion coincidence spectroscopy of radicals produced in a flow tube: OH and OD

    SciTech Connect

    Garcia, Gustavo A.; Tang, Xiaofeng; Gil, Jean-François; Nahon, Laurent; Ward, Michael; Batut, Sebastien; Fittschen, Christa; Taatjes, Craig A.; Osborn, David L.; Loison, Jean-Christophe

    2015-04-28

    We present a microwave discharge flow tube coupled with a double imaging electron/ion coincidence device and vacuum ultraviolet (VUV) synchrotron radiation. The system has been applied to the study of the photoelectron spectroscopy of the well-known radicals OH and OD. The coincidence imaging scheme provides a high selectivity and yields the spectra of the pure radicals, removing the ever-present contributions from excess reactants, background, or secondary products, and therefore obviating the need for a prior knowledge of all possible byproducts. The photoelectron spectra encompassing the X{sup 3}Σ{sup −} ground state of the OH{sup +} and OD{sup +} cations have been extracted and the vibrational constants compared satisfactorily to existing literature values. Future advantages of this approach include measurement of high resolution VUV spectroscopy of radicals, their absolute photoionization cross section, and species/isomer identification in chemical reactions as a function of time.

  11. Synchrotron-based double imaging photoelectron/photoion coincidence spectroscopy of radicals produced in a flow tube: OH and OD

    SciTech Connect

    Garcia, Gustavo A.; Tang, Xiaofeng; Gil, Jean -Francois; Nahon, Laurent; Ward, Michael; Batut, Sebastien; Fittschen, Christa; Taatjes, Craig A.; Osborn, David L.; Loison, Jean -Christophe

    2015-04-23

    In this study, we present a microwave discharge flow tube coupled with a double imaging electron/ion coincidence device and vacuum ultraviolet (VUV) synchrotron radiation. The system has been applied to the study of the photoelectron spectroscopy of the well-known radicals OH and OD. The coincidence imaging scheme provides a high selectivity and yields the spectra of the pure radicals, removing the ever-present contributions from excess reactants, background, or secondary products, and therefore obviating the need for a prior knowledge of all possible byproducts. The photoelectron spectra encompassing the X3Σ ground state of the OH+ and OD+ cations have been extracted and the vibrational constants compared satisfactorily to existing literature values. Future advantages of this approach include measurement of high resolution VUV spectroscopy of radicals, their absolute photoionization cross section, and species/isomer identification in chemical reactions as a function of time.

  12. Dissociative Ionization Mechanism and Appearance Energies in Adipic Acid Revealed by Imaging Photoelectron Photoion Coincidence, Selective Deuteration, and Calculations.

    PubMed

    Heringa, Maarten F; Slowik, Jay G; Prévôt, André S H; Baltensperger, Urs; Hemberger, Patrick; Bodi, Andras

    2016-05-26

    Adipic acid, a model compound for oxygenated organic aerosol, has been studied at the VUV beamline of the Swiss Light Source. Internal energy selected cations were prepared by threshold photoionization using vacuum ultraviolet synchrotron radiation and imaging photoelectron photoion coincidence spectroscopy (iPEPICO). The threshold photoelectron spectrum yields a vertical ionization energy (IE) of 10.5 eV, significantly above the calculated adiabatic IE of 8.6 eV. The cationic minimum is accessible after vertical ionization by H-transfer from one of the γ-carbons to a carbonyl oxygen and is sufficiently energetic to decay by water loss at the ionization onset. The slope of the breakdown curves, quantum chemical calculations, and selective deuteration of the carboxylic hydrogens establish the dissociative photoionization mechanism. After ionization, one γ-methylene hydrogen and the two carboxylic hydrogens are randomized prior to H2O loss. On the basis of the deuteration degree in the H2O + CO-loss product at higher energies, a direct water-loss channel without complete randomization also exists. The breakdown diagram and center of gravity of the H2O + CO-loss peak were modeled to obtain 0 K appearance energies of 10.77, 10.32, and 11.53 eV for H2O + CO loss, CH2COOH loss, and H2O + CH2COOH loss from adipic acid. These agree well with the CBS-QB3 calculated values of 10.68, 10.45, and 11.57 eV, respectively, which shows that threshold photoionization can yield energetics data as long as the dissociation is statistical, even when the parent ion cannot be observed. The results can be used as a starting point for a deeper understanding of the ionization and low-energy fragmentation of organic aerosol components. PMID:27100102

  13. Threshold Photoelectron Photoion Coincidence (TPEPICO) Studies. The Road to ± 0.1 kJ/mol Thermochemistry

    SciTech Connect

    Baer, Tomas

    2013-10-14

    The threshold photoelectron photoion coincidence (TPEPICO) technique is utilized to investigate the dissociation dynamics and thermochemistry of energy selected medium to large organic molecular ions. The reactions include parallel and consecutive steps that are modeled with the statistical theory in order to extract dissociation onsets for multiple dissociation paths. These studies are carried out with the aid of molecular orbital calculations of both ions and the transition states connecting the ion structure to their products. The results of these investigations yield accurate heats of formation of ions, free radicals, and stable molecules. In addition, they provide information about the potential energy surface that governs the dissociation process. Isomerization reactions prior to dissociation are readily inferred from the TPEPICO data.

  14. Dissociation of internal energy-selected methyl bromide ion revealed from threshold photoelectron-photoion coincidence velocity imaging

    NASA Astrophysics Data System (ADS)

    Tang, Xiaofeng; Zhou, Xiaoguo; Sun, Zhongfa; Liu, Shilin; Liu, Fuyi; Sheng, Liusi; Yan, Bing

    2014-01-01

    Dissociative photoionization of methyl bromide (CH3Br) in an excitation energy range of 10.45-16.90 eV has been investigated by using threshold photoelectron-photoion coincidence (TPEPICO) velocity imaging. The coincident time-of-flight mass spectra indicate that the ground state X2E of CH3Br+ is stable, and both A2A1 and B2E ionic excited states are fully dissociative to produce the unique fragment ion of CH3+. From TPEPICO 3D time-sliced velocity images of CH3+ dissociated from specific state-selected CH3Br+ ion, kinetic energy release distribution (KERD) and angular distribution of CH3+ fragment ion are directly obtained. Both spin-orbit states of Br(2P) atom can be clearly observed in fast dissociation of CH3Br+(A2A1) ion along C-Br rupture, while a KERD of Maxwell-Boltzmann profile is obtained in dissociation of CH3Br+(B2E) ion. With the aid of the re-calculated potential energy curves of CH3Br+ including spin-orbit coupling, dissociation mechanisms of CH3Br+ ion in A2A1 and B2E states along C-Br rupture are revealed. For CH3Br+(A2A1) ion, the CH3+ + Br(2P1/2) channel is occurred via an adiabatic dissociation by vibration, while the Br(2P3/2) formation is through vibronic coupling to the high vibrational level of X2E state followed by rapid dissociation. C-Br bond breaking of CH3Br+(B2E) ion can occur via slow internal conversion to the excited vibrational level of the lower electronic states and then dissociation.

  15. 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. PMID:27471793

  16. Dissociation of internal energy-selected methyl bromide ion revealed from threshold photoelectron-photoion coincidence velocity imaging

    SciTech Connect

    Tang, Xiaofeng; Zhou, Xiaoguo E-mail: yanbing@jlu.edu.cn; Liu, Shilin; Sun, Zhongfa; Liu, Fuyi; Sheng, Liusi; Yan, Bing E-mail: yanbing@jlu.edu.cn

    2014-01-28

    Dissociative photoionization of methyl bromide (CH{sub 3}Br) in an excitation energy range of 10.45–16.90 eV has been investigated by using threshold photoelectron-photoion coincidence (TPEPICO) velocity imaging. The coincident time-of-flight mass spectra indicate that the ground state X{sup 2}E of CH{sub 3}Br{sup +} is stable, and both A{sup 2}A{sub 1} and B{sup 2}E ionic excited states are fully dissociative to produce the unique fragment ion of CH{sub 3}{sup +}. From TPEPICO 3D time-sliced velocity images of CH{sub 3}{sup +} dissociated from specific state-selected CH{sub 3}Br{sup +} ion, kinetic energy release distribution (KERD) and angular distribution of CH{sub 3}{sup +} fragment ion are directly obtained. Both spin-orbit states of Br({sup 2}P) atom can be clearly observed in fast dissociation of CH{sub 3}Br{sup +}(A{sup 2}A{sub 1}) ion along C–Br rupture, while a KERD of Maxwell-Boltzmann profile is obtained in dissociation of CH{sub 3}Br{sup +}(B{sup 2}E) ion. With the aid of the re-calculated potential energy curves of CH{sub 3}Br{sup +} including spin-orbit coupling, dissociation mechanisms of CH{sub 3}Br{sup +} ion in A{sup 2}A{sub 1} and B{sup 2}E states along C–Br rupture are revealed. For CH{sub 3}Br{sup +}(A{sup 2}A{sub 1}) ion, the CH{sub 3}{sup +} + Br({sup 2}P{sub 1/2}) channel is occurred via an adiabatic dissociation by vibration, while the Br({sup 2}P{sub 3/2}) formation is through vibronic coupling to the high vibrational level of X{sup 2}E state followed by rapid dissociation. C–Br bond breaking of CH{sub 3}Br{sup +}(B{sup 2}E) ion can occur via slow internal conversion to the excited vibrational level of the lower electronic states and then dissociation.

  17. A threshold photoelectron-photoion coincidence study of the N2O+ dissociation between 15 and 20.5 eV

    NASA Astrophysics Data System (ADS)

    Nenner, Irene; Guyon, Paul-Marie; Baer, Tomas; Govers, Thomas R.

    1980-06-01

    Branching ratios and the kinetic energy released in the various fragmentation channels of energy selected N2O+ (15-20.5 eV) were investigated by the technique of threshold photoelectron-photoion coincidence. Pulsed synchrotron radiation from ACO, Orsay's storage ring, dispersed by a monochromator, was used as a photon source. Threshold electrons were energy selected on the basis of angular and temporal discrimination against energetic electrons. The energy region below 16.388 eV and the ? state were investigated in detail. Below the ? state the most abundant fragment ion is O+, while above the ? state NO+ dominates. Results for the ? and ? states are also reported.

  18. 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.

  19. 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.

  20. 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.

  1. 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

  2. Pulsed field-ionization photoelectron-photoion coincidence study of the process N{sub 2}+h{nu}{yields}N{sup +}+N+e{sup -}: Bond dissociation energies of N{sub 2} and N{sub 2}{sup +}

    SciTech Connect

    Tang Xiaonan; Hou Yu; Ng, C.Y.; Ruscic, Branko

    2005-08-15

    We have examined the dissociative photoionization reaction N{sub 2}+h{nu}{yields}N{sup +}+N+e{sup -} near its threshold using the pulsed field-ionization photoelectron-photoion coincidence (PFI-PEPICO) time-of-flight (TOF) method. By examining the kinetic-energy release based on the simulation of the N{sup +} PFI-PEPICO TOF peak profile as a function of vacuum ultraviolet photon energy and by analyzing the breakdown curves of N{sup +} and N{sub 2}{sup +}, we have determined the 0-K threshold or appearance energy (AE) of this reaction to be 24.2884{+-}0.0010 eV. Using this 0-K AE, together with known ionization energies of N and N{sub 2}, results in more precise values for the 0-K bond dissociation energies of N-N (9.7543{+-}0.0010 eV) and N-N{sup +} (8.7076{+-}0.0010 eV) and the 0-K heats of formation for N (112.469{+-}0.012 kcal/mol) and N{sup +} (447.634{+-}0.012 kcal/mol)

  3. 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.

  4. Photoionization and photoelectron spectroscopy of doped helium nanodroplets

    NASA Astrophysics Data System (ADS)

    Neumark, Daniel

    2006-03-01

    Photoionization and photoelectron spectra for helium nanodroplets doped with rare gas atoms and SF6 will be reported. The experiments were conducted using tunable synchrotron radiation at the Advanced Light Source in the photon energy range of 14-26 eV. Time-of-flight mass spectra will be presented, along with photoion and photoelectron images. The results will be compared to previous electron impact ionization data.

  5. Energy Correlation among Three Photoelectrons Emitted in Core-Valence-Valence Triple Photoionization of Ne

    SciTech Connect

    Hikosaka, Y.; Soejima, K.; Lablanquie, P.; Penent, F.; Palaudoux, J.; Andric, L.; Shigemasa, E.; Suzuki, I. H.; Nakano, M.; Ito, K.

    2011-09-09

    The direct observation of triple photoionization involving one inner shell and two valence electrons is reported. The energy distribution of the three photoelectrons emitted from Ne is obtained using a very efficient multielectron coincidence method using the magnetic bottle electron spectroscopic technique. A predominance of the direct path to triple photoionization for the formation of Ne{sup 3+} in the 1s2s{sup 2}2p{sup 4} configuration is observed. It is demonstrated that the energy distribution evolves with photon energy and indicates a significant difference with triple photoionization involving only valence electrons.

  6. Energy Correlation among Three Photoelectrons Emitted in Core-Valence-Valence Triple Photoionization of Ne

    NASA Astrophysics Data System (ADS)

    Hikosaka, Y.; Lablanquie, P.; Penent, F.; Palaudoux, J.; Andric, L.; Soejima, K.; Shigemasa, E.; Suzuki, I. H.; Nakano, M.; Ito, K.

    2011-09-01

    The direct observation of triple photoionization involving one inner shell and two valence electrons is reported. The energy distribution of the three photoelectrons emitted from Ne is obtained using a very efficient multielectron coincidence method using the magnetic bottle electron spectroscopic technique. A predominance of the direct path to triple photoionization for the formation of Ne3+ in the 1s2s22p4 configuration is observed. It is demonstrated that the energy distribution evolves with photon energy and indicates a significant difference with triple photoionization involving only valence electrons.

  7. Energy correlation among three photoelectrons emitted in core-valence-valence triple photoionization of Ne.

    PubMed

    Hikosaka, Y; Lablanquie, P; Penent, F; Palaudoux, J; Andric, L; Soejima, K; Shigemasa, E; Suzuki, I H; Nakano, M; Ito, K

    2011-09-01

    The direct observation of triple photoionization involving one inner shell and two valence electrons is reported. The energy distribution of the three photoelectrons emitted from Ne is obtained using a very efficient multielectron coincidence method using the magnetic bottle electron spectroscopic technique. A predominance of the direct path to triple photoionization for the formation of Ne3+ in the 1s 2s2 2p4 configuration is observed. It is demonstrated that the energy distribution evolves with photon energy and indicates a significant difference with triple photoionization involving only valence electrons. PMID:22026663

  8. Double photoionization of SO 2 and fragmentation spectroscopy of SO 2++ studied by a photoion-photoion coincidence method

    NASA Astrophysics Data System (ADS)

    Dujardin, Gérald; Leach, Sydney; Dutuit, Odile; Guyon, Paul-Marie; Richard-Viard, Martine

    1984-08-01

    Doubly charged sulphur dioxide cations (SO 2++) are produced by photoionization with synchrotron radiation from ACO in the excitation-energy range 34-54 eV. A new photoion-photoion coincidence (PIPICO) experiment is described in which coincidences between photoion fragments originating from the dissociation of the doubly charged parent cation are counted. This PIPICO method enables us to study the fragmentation of individual electronically excited states of SO 2++ and to determine the corresponding absolute double-photoionization partial cross sections as a function of the excitation energy. A tentative assignment of the three observed α, β and γ SO 2++ states is given. The dissociation processes of the α and β states into the products SO + + O + are found to be non-statistical in nature; the γ state dissociates completely into three atomic fragments S + + O + + O. Three main observed features of the double-photoionization cross-section curves are discussed in the text: appearance potentials, linear threshold laws, and constant double-photoionization cross sections relative to the total ionization cross section at high energies.

  9. Photoelectron wave function in photoionization: plane wave or Coulomb wave?

    PubMed

    Gozem, Samer; Gunina, Anastasia O; Ichino, Takatoshi; Osborn, David L; Stanton, John F; Krylov, Anna I

    2015-11-19

    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 photoelectron 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. 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. PMID:26509428

  10. Imaging photoelectron circular dichroism of chiral molecules by femtosecond multiphoton coincidence detection

    SciTech Connect

    Lehmann, C. Stefan; Ram, N. Bhargava; Janssen, Maurice H. M.; Powis, Ivan

    2013-12-21

    Here, we provide a detailed account of novel experiments employing electron-ion coincidence imaging to discriminate chiral molecules. The full three-dimensional angular scattering distribution of electrons is measured after photoexcitation with either left or right circular polarized light. The experiment is performed using a simplified photoelectron-photoion coincidence imaging setup employing only a single particle imaging detector. Results are reported applying this technique to enantiomers of the chiral molecule camphor after three-photon ionization by circularly polarized femtosecond laser pulses at 400 nm and 380 nm. The electron-ion coincidence imaging provides the photoelectron spectrum of mass-selected ions that are observed in the time-of-flight mass spectra. The coincident photoelectron spectra of the parent camphor ion and the various fragment ions are the same, so it can be concluded that fragmentation of camphor happens after ionization. We discuss the forward-backward asymmetry in the photoelectron angular distribution which is expressed in Legendre polynomials with moments up to order six. Furthermore, we present a method, similar to one-photon electron circular dichroism, to quantify the strength of the chiral electron asymmetry in a single parameter. The circular dichroism in the photoelectron angular distribution of camphor is measured to be 8% at 400 nm. The electron circular dichroism using femtosecond multiphoton excitation is of opposite sign and about 60% larger than the electron dichroism observed before in near-threshold one-photon ionization with synchrotron excitation. We interpret our multiphoton ionization as being resonant at the two-photon level with the 3s and 3p Rydberg states of camphor. Theoretical calculations are presented that model the photoelectron angular distribution from a prealigned camphor molecule using density functional theory and continuum multiple scattering X alpha photoelectron scattering calculations

  11. Imaging photoelectron circular dichroism of chiral molecules by femtosecond multiphoton coincidence detection

    NASA Astrophysics Data System (ADS)

    Lehmann, C. Stefan; Ram, N. Bhargava; Powis, Ivan; Janssen, Maurice H. M.

    2013-12-01

    Here, we provide a detailed account of novel experiments employing electron-ion coincidence imaging to discriminate chiral molecules. The full three-dimensional angular scattering distribution of electrons is measured after photoexcitation with either left or right circular polarized light. The experiment is performed using a simplified photoelectron-photoion coincidence imaging setup employing only a single particle imaging detector. Results are reported applying this technique to enantiomers of the chiral molecule camphor after three-photon ionization by circularly polarized femtosecond laser pulses at 400 nm and 380 nm. The electron-ion coincidence imaging provides the photoelectron spectrum of mass-selected ions that are observed in the time-of-flight mass spectra. The coincident photoelectron spectra of the parent camphor ion and the various fragment ions are the same, so it can be concluded that fragmentation of camphor happens after ionization. We discuss the forward-backward asymmetry in the photoelectron angular distribution which is expressed in Legendre polynomials with moments up to order six. Furthermore, we present a method, similar to one-photon electron circular dichroism, to quantify the strength of the chiral electron asymmetry in a single parameter. The circular dichroism in the photoelectron angular distribution of camphor is measured to be 8% at 400 nm. The electron circular dichroism using femtosecond multiphoton excitation is of opposite sign and about 60% larger than the electron dichroism observed before in near-threshold one-photon ionization with synchrotron excitation. We interpret our multiphoton ionization as being resonant at the two-photon level with the 3s and 3p Rydberg states of camphor. Theoretical calculations are presented that model the photoelectron angular distribution from a prealigned camphor molecule using density functional theory and continuum multiple scattering X alpha photoelectron scattering calculations

  12. K-shell photoionization of CO: I. Angular distributions of photoelectrons from fixed-in-space molecules

    NASA Astrophysics Data System (ADS)

    Motoki, S.; Adachi, J.; Hikosaka, Y.; Ito, K.; Sano, M.; Soejima, K.; Yagishita, A.; Raseev, G.; Cherepkov, N. A.

    2000-10-01

    Angular distributions of photoelectrons from both C and O K-shells of the fixed-in-space CO molecule have been measured using the angle-resolved photoelectron-photoion coincidence technique. The measurements have been performed at several photon energies from the ionization thresholds up to about 30 eV above them, where the σ* shape resonances occur. Experimental results are compared with the multiple-scattering calculations of Dill et al (1976 J. Chem. Phys. 65 3158) and with our new calculations in the relaxed-core Hartree-Fock approximation. Our calculations are in a better agreement with the experimental data though numerical discrepancies remain. The experimental angular distributions are fitted by the expansion in Legendre polynomials containing up to ten terms and the extracted parameters are compared with the corresponding theoretical values.

  13. Multi-electron coincidence spectroscopy: double photoionization from molecular inner-shell orbitals

    NASA Astrophysics Data System (ADS)

    Hikosaka, Y.; Lablanquie, P.; Penent, F.; Nakano, M.; Ito, K.

    2014-04-01

    We have studied double photoionization from molecular inner-shell orbitals and investigated the properties of the resultant double core-hole states in molecules, by multi-electron coincidence spectroscopy with a magnetic bottle electron spectrometer. A brief summary of our previous studies is presented.

  14. Fragmentation of doubly charged ammonia cations NH{3/++} studied by the photoion-photoion coincidence (PIPICO) method

    NASA Astrophysics Data System (ADS)

    Winkoun, D.; Dujardin, G.

    1986-03-01

    Doubly charged NH{3/++} cations were produced by double photoionization of neutral ammonia molecules by using the synchrotron radiation from ACO as a photon source of variable energy in the 35 49 eV energy range. The fragmentation of NH{3/++} was studied by the photoion-photoion coincidence (PIPICO) method. NH{3/++} cations were produced in thetilde X^1 A 1 andtilde B^1 electronic states of which the onset energies were measured at, respectively, 35.4±0.5 eV and 44.5±0.5 eV. It was shown that the NH{3/++} ions, initially produced in theirtilde X^1 A 1 state, rapidly dissociate (in less than 50 ns), into NH{2/+} + H+. Furthermore, the comparison with results obtained by other methods indicates that NH{3/++} ions can either be long-lived (τ>10 µs) or slowly dissociating (1 µs<τ<10 µs) or rapidly dissociating (τ<50 ns), depending on their geometry and/or internal energy in theirtilde X^1 E A 1 electronic state.

  15. High-Resolution Threshold Photoionization and Photoelectron Spectroscopy of Propene and 2-BUTYNE

    NASA Astrophysics Data System (ADS)

    Michaud, Julie M.; Vasilatou, Konstantina; Merkt, Frédéric

    2009-06-01

    The high-resolution photoionization and pulsed-field ionization zero-kinetic energy (PFI-ZEKE) photoelectron spectra of propene and 2-butyne and their perdeuterated isotopologues have been recorded in the vicinity of the first adiabatic ionization energy following single-photon excitation from the neutral ground state using a narrowband vacuum ultraviolet laser system. The spectral resolution of better than 0.1 cm^{-1} achieved in these spectra has enabled us to partially resolve the rotational structure of the photoelectron spectra and to obtain information on the internal rotation/torsional vibration of the methyl groups in the cationic ground state. The intensity distributions observed in the photoelectron spectra will be discussed in terms of rovibronic photoionization selection rules and Franck-Condon factors for transitions between the neutral and ionized molecules.

  16. 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

  17. 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.

  18. 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.

  19. Rotationally resolved photoelectron spectroscopy of a triatomic molecule: Photoionization of the C (0.0.0) state of water

    SciTech Connect

    Glab, W.L.; Glynn, P.T.; Dehmer, P.M.; Dehmer, J.L.

    1996-05-01

    The authors have used a magnetic bottle photoelectron spectrometer to study the distribution of ion rotational states following photoionization of selected rotational states of the {tilde C}(0,0,0) state of water by 355 nm light. The spectrometer`s kinetic energy resolution of about 4 meV was sufficient to yield rotationally resolved time-of-flight photoelectron spectra. Comparison of the measured and calculated photoelectron spectra is encouraging and reveals unusual photoionization dynamics due to very nonatomic-like behavior in the photoionization continuum and to the presence of Cooper minima. This is the first time that such a test of photoionization theory for a polyatomic molecule at finite kinetic energy has been possible.

  20. Development of an Apparatus for High-Resolution Auger Photoelectron Coincidence Spectroscopy (APECS) and Electron Ion Coincidence (EICO) Spectroscopy

    NASA Astrophysics Data System (ADS)

    Kakiuchi, Takuhiro; Hashimoto, Shogo; Fujita, Narihiko; Mase, Kazuhiko; Tanaka, Masatoshi; Okusawa, Makoto

    We have developed an electron electron ion coincidence (EEICO) apparatus for high-resolution Auger photoelectron coincidence spectroscopy (APECS) and electron ion coincidence (EICO) spectroscopy. It consists of a coaxially symmetric mirror electron energy analyzer (ASMA), a miniature double-pass cylindrical mirror electron energy analyzer (DP-CMA), a miniature time-of-flight ion mass spectrometer (TOF-MS), a magnetic shield, an xyz stage, a tilt-adjustment mechanism, and a conflat flange with an outer diameter of 203 mm. A sample surface was irradiated by synchrotron radiation, and emitted electrons were energy-analyzed and detected by the ASMA and the DP-CMA, while desorbed ions were mass-analyzed and detected by the TOF-MS. The performance of the new EEICO analyzer was evaluated by measuring Si 2p photoelectron spectra of clean Si(001)-2×1 and Si(111)-7×7, and by measuring Si-L23VV-Si-2p Auger photoelectron coincidence spectra (Si-L23VV-Si-2p APECS) of clean Si(001)-2×1.

  1. Photoionization study of Xe 5s: ionization cross sections and photoelectron angular distributions

    NASA Astrophysics Data System (ADS)

    Aarthi, G.; Jose, J.; Deshmukh, S.; Radojevic, V.; Deshmukh, P. C.; Manson, S. T.

    2014-01-01

    We report studies of photoelectron angular distribution and cross-section for photoionization of xenon 5s electrons using the relativistic multiconfiguration Tamm-Dancoff (MCTD) approximation. We find that MCTD provides a significantly improved agreement with experiment, compared to some of the other relativistic many body approximations such as the relativistic random phase approximation and the relativistic random phase approximation with relaxation, over the entire photon energy region bracketing the near-threshold 5s Cooper minimum, from the 5s threshold up to about 70 eV. The MCTD results in the length form are in much better agreement with the experiment than those in the velocity form, suggesting residual correlations that must be of importance.

  2. PHOTOELECTRON AND AUGER ELECTRON ASYMMETRIES: ALIGNMENT OF Xe{sup +}({sup 2}D{sub 5/2}) BY PHOTOIONIZATION

    SciTech Connect

    Southworth, S. H.; Kobrin, P. H.; Truesdale, C. M.; Lindle, D.; Owaki, S.; Shirley, D. A.

    1980-12-01

    Angular distributions of photoelectrons from the Xe 4d subshell, and N{sub 4,5}oo Auger electrons, have been measured using synchrotron radiation. The 4d asymmetry parameter exhibits strong oscillations with energy, in agreement with several theoretical calculations. The Auger electrons show large asymmetries due to alignment of Xe{sup +} by photoionization.

  3. Rovibronically Selected and Resolved Laser Photoionization and Photoelectron Studies of Transition Metal Carbides, Nitrides, and Oxides.

    NASA Astrophysics Data System (ADS)

    Luo, Zhihong; Chang, Yih-Chung; Huang, Huang; Ng, Cheuk-Yiu

    2014-06-01

    Transition metal (M) carbides, nitrides, and oxides (MX, X = C, N, and O) are important molecules in astrophysics, catalysis, and organometallic chemistry. The measurements of the ionization energies (IEs), bond energies, and spectroscopic constants for MX/MX+ in the gas phase by high-resolution photoelectron methods represent challenging but profitable approaches to gain fundamental understandings of the electronic structures and bonding properties of these compounds and their cations. We have developed a two-color laser excitation scheme for high-resolution pulse field ionization photoelectron (PFI-PE) measurements of MX species. By exciting the neutral MX species to a single rovibronic state using a visible laser prior to photoionization by a UV laser, we have obtained fully rotational resolved PFI-PE spectra for TiC+, TiO+, VCH+, VN+, CoC+, ZrO+, and NbC+. The unambiguous rotational assignments of these spectra have provided highly accurate IE values for TiC, TiO, VCH, VN, CoC, ZrO, and NbC, and spectroscopic constants for their cations.

  4. Stability and dissociation dynamics of N2 (++) ions following core ionization studied by an Auger-electron-photoion coincidence method.

    PubMed

    Iwayama, H; Kaneyasu, T; Hikosaka, Y; Shigemasa, E

    2016-07-21

    An Auger-electron-photoion coincidence (AEPICO) method has been applied to study the stability and dissociation dynamics of dicationic states after the N K-shell photoionization of nitrogen molecules. From time-of-flight and kinetic energy analyses of the product ions, we have obtained coincident Auger spectra associated with metastable states of N2 (++) ions and dissociative states leading to N2 (++) → N(+) + N(+) and N(++) + N. To investigate the production of dissociative states, we present two-dimensional AEPICO maps which reveal the correlations between the binding energies of the Auger final states and the ion kinetic energy release. These correlations have been used to determine the dissociation limits of individual Auger final states. PMID:27448885

  5. Photoelectron imaging of XUV photoionization of CO2 by 13-40 eV synchrotron radiation

    NASA Astrophysics Data System (ADS)

    Furch, Federico J.; Birkner, Sascha; Jungmann, Julia H.; Kelkensberg, Freek; Schulz, Claus Peter; Rouzée, Arnaud; Vrakking, Marc J. J.

    2013-09-01

    Valence band photoionization of CO2 has been studied by photoelectron spectroscopy using a velocity map imaging spectrometer and synchrotron radiation. The measured data allow retrieving electronic and vibrational branching ratios, vibrationally resolved asymmetry parameters, and the total electron yield which includes multiple strong resonances. Additionally, the spectrum of low kinetic energy electrons has been studied in the resonant region, and the evolution with photon energy of one of the forbidden transitions present in the slow photoelectrons spectrum has been carefully analyzed, indicating that in the presence of auto-ionizing resonances the vibrational populations of the ion are significantly redistributed.

  6. 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.

  7. Auger, zero-energy photoelectron, coincidence spectroscopy (AZEPECO): Chemical-site-selective Auger electron spectroscopy

    SciTech Connect

    Lee, K.; Ji, D.; Hanson, D.M.; Hulbert, S.L.; Kuiper, P.

    1993-12-31

    The Auger electron spectrum associated with decay of a core-hole on the terminal nitrogen and that associated with the central nitrogen of nitrous oxide, N{sub 2}O, are obtained individually through the use of a coincidence technique. Specifically, each of the two Auger electron spectra is obtained by detection of Auger electrons in coincidence with near zero energy (threshold) photoelectrons at the respective ionization thresholds. These zero energy electrons serve to identify the core-ionization continuum associated with the different Auger electrons. The salient features of the experimental spectra are in good agreement with theoretical calculations. The low counting rate generally associated with coincidence experiments, especially in the gas phase, is not encountered because the low energy electrons are collected over a 4{pi} solid angle. Also, velocity discrimination is accomplished by a spatial filter rather than by time-of-flight to utilize the maximum duty cycle of the synchrotron source. These data are believed to be the first examples of chemical-site-selective molecular Auger spectra.

  8. 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.

  9. Communication: State-to-state photoionization and photoelectron study of vanadium methylidyne radical (VCH)

    SciTech Connect

    Luo, Zhihong; Zhang, Zheng; Huang, Huang; Chang, Yih-Chung; Ng, C. Y.

    2014-05-14

    By employing the infrared (IR)-ultraviolet (UV) laser excitation scheme, we have obtained rotationally selected and resolved pulsed field ionization-photoelectron (PFI-PE) spectra for vanadium methylidyne cation (VCH{sup +}). This study supports that the ground state electronic configuration for VCH{sup +} is …7σ{sup 2}8σ{sup 2}3π{sup 4}9σ{sup 1} (X{sup ~2}Σ{sup +}), and is different from that of …7σ{sup 2}8σ{sup 2}3π{sup 4}1δ{sup 1} (X{sup ~2}Δ) for the isoelectronic TiO{sup +} and VN{sup +} ions. This observation suggests that the addition of an H atom to vanadium carbide (VC) to form VCH has the effect of stabilizing the 9σ orbital relative to the 1δ orbital. The analysis of the state-to-state IR-UV-PFI-PE spectra has provided precise values for the ionization energy of VCH, IE(VCH) = 54 641.9 ± 0.8 cm{sup −1} (6.7747 ± 0.0001 eV), the rotational constant B{sup +} = 0.462 ± 0.002 cm{sup −1}, and the v{sub 2}{sup +} bending (626 ± 1 cm{sup −1}) and v{sub 3}{sup +} V–CH stretching (852 ± 1 cm{sup −1}) vibrational frequencies for VCH{sup +}(X{sup ~2}Σ{sup +}). The IE(VCH) determined here, along with the known IE(V) and IE(VC), allows a direct measure of the change in dissociation energy for the V–CH as well as the VC–H bond upon removal of the 1δ electron of VCH(X{sup ~3}Δ{sub 1}). The formation of VCH{sup +}(X{sup ~2}Σ{sup +}) from VCH(X{sup ~3}Δ{sub 1}) by photoionization is shown to strengthen the VC–H bond by 0.3559 eV, while the strength of the V–CH bond remains nearly unchanged. This measured change of bond dissociation energies reveals that the highest occupied 1δ orbital is nonbonding for the V–CH bond; but has anti-bonding or destabilizing character for the VC–H bond of VCH(X{sup ~3}Δ{sub 1})

  10. Dynamical Relativistic Effects in Photoionization: Spin-Orbit-Resolved Angular Distributions of Xenon 4d Photoelectrons near the Cooper Minimum

    SciTech Connect

    Wang, H.; Snell, G.; Hemmers, O.; Sant'Anna, M. M.; Sellin, I.; Berrah, N.; Lindle, D. W.; Deshmukh, P. C.; Haque, N.; Manson, S. T.

    2001-09-17

    Two decades ago, it was predicted [Y.S.Kim et al., Phys.Rev.Lett.46, 1326 (1981)] that relativistic effects should alter the dynamics of the photoionization process in the vicinity of Cooper minima. The present experimental and theoretical study of the angular distributions of Xe 4d{sub 3/2} and 4d{sub 5/2} photoelectrons demonstrates this effect for the first time. The results clearly imply that relativistic effects are likely to be important for intermediate-Z atoms at most energies.

  11. Photoelectron-photofragment coincidence spectroscopy in a cryogenically cooled linear electrostatic ion beam trap

    SciTech Connect

    Johnson, Christopher J.; Shen, Ben B.; Poad, Berwyck L. J.; Continetti, Robert E.

    2011-10-15

    A cryogenically cooled linear electrostatic ion beam trap for use in photoelectron-photofragment coincidence (PPC) spectroscopy is described. Using this instrument, anions created in cold, low-duty-cycle sources can be stored for many seconds in a {approx}20 K environment to cool radiatively, removing energetic uncertainties due to vibrationally excited precursor anions. This apparatus maintains a well-collimated beam necessary for high-resolution fragment imaging and the high experimental duty cycle needed for coincidence experiments. Ion oscillation is bunched and phase-locked to a modelocked laser, ensuring temporal overlap between ion bunches and laser pulses and that ions are intersected by the laser only when travelling in one direction. An electron detector is housed in the field-free center of the trap, allowing PPC experiments to be carried out on ions while they are stored and permitting efficient detection of 3-dimensional electron and neutral recoil trajectories. The effects of trapping parameters on the center-of-mass trajectories in the laser-ion interaction region are explored to optimize neutral particle resolution, and the impact of bunching on ion oscillation is established. Finally, an initial demonstration of radiative cooling is presented.

  12. Enantioselective femtosecond laser photoionization spectrometry of limonene using photoelectron circular dichroism.

    PubMed

    Rafiee Fanood, Mohammad M; Janssen, Maurice H M; Powis, Ivan

    2015-04-14

    Limonene is ionized by circularly polarized 420 nm femtosecond laser pulses. Ion mass and photoelectron energy spectra identify the dominant (2 + 1) multiphoton ionization mechanism, aided by TDDFT calculations of the Rydberg excitations. Photoelectron circular dichroism measurements on pure enantiomers reveal a chiral asymmetry of ±4 %. PMID:25744283

  13. Molecular photoionization studies

    SciTech Connect

    Dehmer, P.M.

    1983-01-01

    This program is concerned with the study of the electronic structure of small molecules and clusters of molecules. Of particular interest is the interaction of discrete electronic states with one another and with the various ionization and dissociation continua. Since the Second Annual Meeting of the DOE-OHER Program on The Physics and Chemistry of Energy-Related Atmospheric Pollutants in April 1981, significant progress has been made in the following areas: (1) the study of the electronic structure of dimers and small clusters of rare gas atoms using photoionization techniques; (2) similar studies on clusters of CO/sub 2/ molecules; (3) the study of electronic structure of rare gas dimers and trimers using photoelectron and photoelectron-photoion coincidence techniques; (4) the investigation of the relationship between Rydberg states in atoms, van der Waals molecules, and chemically-bonded molecules; (5) the extension of the study of photoabsorption, photoionization, and predissociation processes in H/sub 2/ to the unsymmetric isotope HD; (6) the study of photoelectron spectra of H/sub 2/ and C/sub 2/H/sub 2/; (7) a review of some of the aspects of dissociation processes in small molecules; and (8) the creation of a new program to study the spectra and dynamics of the photoionization processes in small molecules using the technique of multiphoton ionization followed by mass and electron energy analysis of the product ions and electrons. Some of the highlights of this work are reviewed.

  14. Probing photoelectron multiple interferences via Fourier spectroscopy in energetic photoionization of Xe-C{sub 60}

    SciTech Connect

    Potter, Andrea; McCune, Matthew A.; De, Ruma; Chakraborty, Himadri S.; Madjet, Mohamed E.

    2010-09-15

    Considering the photoionization of the Xe-C{sub 60} endohedral compound, we study in detail the ionization cross sections of various levels of the system at energies higher than the plasmon resonance region. Five classes of single-electron levels are identified depending on their spectral character. Each class engenders distinct oscillations in the cross section, emerging from the interference between active ionization modes specific to that class. Analysis of the cross sections based on their Fourier transforms unravels oscillation frequencies that carry unique fingerprints of the emitting level.

  15. Photoionization of He above the N =2 threshold. II. Angular distribution of photoelectrons and asymmetry parameter

    SciTech Connect

    Sanchez, I.; Martin, F. )

    1992-04-01

    We report theoretical calculations for the {beta}{sub 2{ital p}}-asymmetry parameter in the photoionization of He(1{ital s}{sup 2}) above the {ital N}=2 ionization threshold. We use an extension of a method recently proposed (I. Sanchez and F. Martin, Phys. Rev. A 44, 7318 (1991)) that makes use of a Feshbach partitioning of the final-state wave function and an {ital L}{sup 2} representation of the coupled continuum states. Partial differential cross sections at emission angles 0{degree} and 90{degree} are also provided. Our results are in good agreement with the experimental data, thus showing the accuracy of the present method to study electron angular-distribution properties.

  16. A HIGH-RESOLUTION PHOTOIONIZATION AND PHOTOELECTRON STUDY OF {sup 58}Ni USING A VACUUM ULTRAVIOLET LASER

    SciTech Connect

    Shi Xiaoyu; Huang Huang; Jacobson, Brian; Chang, Yih-Chung; Ng, C. Y.; Yin Qingzhu

    2012-03-01

    In order to provide high-resolution spectroscopic data of nickel ({sup 58}Ni) and its cation ({sup 58}Ni{sup +}) for the assignment of vacuum ultraviolet (VUV) stellar spectra, we have obtained the photoionization efficiency (PIE) spectra of {sup 58}Ni by using a supersonically cooled laser ablation transition-metal beam source and a broadly tunable VUV laser in the range of 61,100-73,600 cm{sup -1}, covering the photoionization transitions: Ni{sup +} (3d{sup 92} D) <- Ni (3d{sup 8}4s{sup 23} D), Ni{sup +}(3d{sup 92} D) <- Ni(3d{sup 8}4s{sup 23} F), and Ni{sup +} (3d{sup 8}4s{sup 4} F) <- Ni(3d{sup 8}4s{sup 23} F). We have also measured the VUV laser pulsed-field-ionization-photoelectron (PFI-PE) spectra of {sup 58}Ni in these regions. The VUV-PFI-PE measurement has allowed the determination of a precise value of 61,619.89 {+-} 0.8 cm{sup -1} (7.6399 {+-} 0.0001 eV) for the ionization energy (IE) of {sup 58}Ni. Due to the narrow VUV laser optical bandwidth of 0.4 cm{sup -1} used in the present study, many complex autoionizing resonances exhibiting Fano line shape profiles are resolved in the PIE spectra. Four autoionizing Rydberg series originating from two-electron and one-electron excitations from the Ni(3d{sup 8}4s{sup 23} F{sub 4}) ground state to converge to the respective Ni{sup +}({sup 2} D{sub 3/2}) and Ni{sup +}({sup 4} F{sub J} ) (J = 9/2, 7/2, and 5/2) ion states are identified. The Rydberg analysis, along with VUV-PFI-PE measurements, has yielded highly precise IE values for the formation of these excited ionic states from the Ni(3d{sup 8}4s{sup 23} F{sub 4}) ground state. The IE values, relative photoionization cross sections, and autoionizing Rydberg resonances observed in the present study are relevant to astrophysics by enhancing the atomic database of iron group transition metal atoms and for understanding the Ni and Ni{sup +} contribution to the VUV opacity in the solar atmosphere.

  17. 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.

  18. PCI effects and the gradual formation of Rydberg series due to photoelectron recapture, in the Auger satellite lines upon Xe 4d-15/2 photoionization

    NASA Astrophysics Data System (ADS)

    Kosugi, Satoshi; Iizawa, Masatomi; Kawarai, Yu; Kuriyama, Yosuke; Kilcoyne, A. L. David; Koike, Fumihiro; Kuze, Nobuhiko; Slaughter, Daniel S.; Azuma, Yoshiro

    2015-06-01

    The Xe (N5O2,3O2,3) Auger electron spectra originating from 4d-15/2 inner-shell photoionization were measured, with photon energy tuned close to the ionization threshold. As the photon energy approaches the threshold from above the 4d-15/2 photoionization threshold, Rydberg series structures are formed within the Auger electron peak by the recapture of the photoelectron into high-lying ion orbitals. They emerge in the tail on the higher energy side of the post-collision interaction (PCI) profile of the Auger electron. Discrete Rydberg peaks replace the continuous PCI tail and gradually form a series with intensity distribution emulating the intensity profile of the continuous tail. Structures due to the Xe+5p4(1S0, 1D2, 3P2,1,0) ml series were observed and assigned.

  19. THE ELECTRONIC STRUCTURE OF AG/CU(100) SURFACE ALLOYS STUDIES BY AUGER-PHOTOELECTRON COINCIDENCE SPECTROSCOPY.

    SciTech Connect

    ARENA,D.A.; BARTYNSKI,R.A.; HULBERT,S.L.

    2001-10-08

    We have measured the Ag and Pd M{sub 5}VV Auger spectrum in coincidence with Ag and Pd 4d{sub 5/2} photoelectrons for the Ag/Cu(100) and Pd/Cu(100) systems, respectively, as a function of admetal coverage. These systems form surface alloys (i.e. random substitutional alloys in the first atomic layer) for impurity concentrations in the 0.1 monolayer range. For these systems, the centroid of the impurity 4d levels is expected to shift away from the Fermi level by {approx}1 eV [Ruban et al., Journal of Molecular Catalysis. A 115 (1997) 421], an effect that should be easily seen in coincidence core-valence-valence Auger spectra. We find that the impurity Auger spectra of both systems shift in a manner that is consistent with d-band moving away from EF. However, the shift for Pd is considerably smaller than expected, and a shift almost absent for Ag. The disagreement between theory and experiment is most likely caused by the neglect of lattice relaxations in the calculations.

  20. 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.

  1. Development of a miniature double-pass cylindrical mirror electron energy analyzer (DPCMA), and its application to Auger photoelectron coincidence spectroscopy (APECS)

    NASA Astrophysics Data System (ADS)

    Kobayashi, Eiichi; Seo, Junya; Nambu, Akira; Mase, Kazuhiko

    2007-09-01

    We have developed a miniature double-pass cylindrical mirror electron energy analyzer (DPCMA) with an outer diameter of 26 mm. The DPCMA consists of a shield for the electric field, inner and outer cylinders, two pinholes with a diameter of 2.0 mm, and an electron multiplier. By assembling the DPCMA in a coaxially symmetric mirror electron energy analyzer (ASMA) coaxially and confocally we developed an analyzer for Auger photoelectron coincidence spectroscopy (APECS). The performance was estimated by measuring the Si-LVV-Auger Si-1s-photoelectron coincidence spectra of clean Si(1 1 1). The electron-energy resolution of the DPCMA was estimated to be E/Δ E = 20. This value is better than that of the miniature single-pass CMA ( E/Δ E = 12) that was used in the previous APECS analyzer.

  2. 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.

  3. 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. PMID:26980311

  4. 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.

  5. Rotationally resolved state-to-state photoionization and photoelectron study of titanium carbide and its cation (TiC/TiC{sup +})

    SciTech Connect

    Luo, Zhihong; Huang, Huang; Chang, Yih-Chung; Zhang, Zheng; Ng, C. Y.; Yin, Qing-Zhu

    2014-10-14

    Titanium carbide and its cation (TiC/TiC{sup +}) have been investigated by the two-color visible (VIS)-ultraviolet (UV) resonance-enhanced photoionization and pulsed field ionization-photoelectron (PFI-PE) methods. Two visible excitation bands for neutral TiC are observed at 16 446 and 16 930 cm{sup −1}. Based on rotational analyses, these bands are assigned as the respective TiC({sup 3}Π{sub 1}) ← TiC(X{sup 3}Σ{sup +}) and TiC({sup 3}Σ{sup +}) ← TiC(X{sup 3}Σ{sup +}) transition bands. This assignment supports that the electronic configuration and term symmetry for the neutral TiC ground state are …7σ{sup 2}8σ{sup 1}9σ{sup 1}3π{sup 4} (X{sup 3}Σ{sup +}). The rotational constant and the corresponding bond distance of TiC(X{sup 3}Σ{sup +}; v″ = 0) are determined to be B{sub 0}″ = 0.6112(10) cm{sup −1} and r{sub 0}″ = 1.695(2) Å, respectively. The rotational analyses of the VIS-UV-PFI-PE spectra for the TiC{sup +}(X; v{sup +} = 0 and 1) vibrational bands show that the electronic configuration and term symmetry for the ionic TiC{sup +} ground state are …7σ{sup 2}8σ{sup 1}3π{sup 4} (X{sup 2}Σ{sup +}) with the v{sup +} = 0 → 1 vibrational spacing of 870.0(8) cm{sup −1} and the rotational constants of B{sub e}{sup +} = 0.6322(28) cm{sup −1}, and α{sub e}{sup +} = 0.0085(28) cm{sup −1}. The latter rotational constants yield the equilibrium bond distance of r{sub e}{sup +} = 1.667(4) Å for TiC{sup +}(X{sup 2}Σ{sup +}). The cleanly rotationally resolved VIS-UV-PFI-PE spectra have also provided a highly precise value of 53 200.2(8) cm{sup −1} [6.5960(1) eV] for the adiabatic ionization energy (IE) of TiC. This IE(TiC) value along with the known IE(Ti) has made possible the determination of the difference between the 0 K bond dissociation energy (D{sub 0}) of TiC{sup +}(X{sup 2}Σ{sup +}) and that of TiC(X{sup 3}Σ{sup +}) to be D{sub 0}(Ti{sup +}−C) − D{sub 0}(Ti−C) = 0.2322(2) eV. Similar to previous experimental

  6. On the absolute photoionization cross section and dissociative photoionization of cyclopropenylidene.

    PubMed

    Holzmeier, Fabian; Fischer, Ingo; Kiendl, Benjamin; Krueger, Anke; Bodi, Andras; Hemberger, Patrick

    2016-04-01

    We report the determination of the absolute photoionization cross section of cyclopropenylidene, c-C3H2, and the heat of formation of the C3H radical and ion derived by the dissociative ionization of the carbene. Vacuum ultraviolet (VUV) synchrotron radiation as provided by the Swiss Light Source and imaging photoelectron photoion coincidence (iPEPICO) were employed. Cyclopropenylidene was generated by pyrolysis of a quadricyclane precursor in a 1 : 1 ratio with benzene, which enabled us to derive the carbene's near threshold absolute photoionization cross section from the photoionization yield of the two pyrolysis products and the known cross section of benzene. The cross section at 9.5 eV, for example, was determined to be 4.5 ± 1.4 Mb. Upon dissociative ionization the carbene decomposes by hydrogen atom loss to the linear isomer of C3H(+). The appearance energy for this process was determined to be AE(0K)(c-C3H2; l-C3H(+)) = 13.67 ± 0.10 eV. The heat of formation of neutral and cationic C3H was derived from this value via a thermochemical cycle as Δ(f)H(0K)(C3H) = 725 ± 25 kJ mol(-1) and Δ(f)H(0K)(C3H(+)) = 1604 ± 19 kJ mol(-1), using a previously reported ionization energy of C3H. PMID:26975696

  7. A new double imaging velocity focusing coincidence experiment: i{sup 2}PEPICO

    SciTech Connect

    Bodi, Andras; Hemberger, Patrick; Gerber, Thomas; Sztaray, Balint

    2012-08-15

    The vacuum ultraviolet (VUV) beamline of the Swiss Light Source has been upgraded after two years of operation. A new, turntable-type monochromator was constructed at the Paul Scherrer Institut, which allows for fast yaw-alignment as well as quick grating change and exchange. In addition to the original imaging photoelectron photoion coincidence endstation (iPEPICO), a second, complementary double imaging setup (i{sup 2}PEPICO) has been built. Volatile samples can be introduced at room temperature or in a molecular beam, a pyrolysis source allows for radical production, and non-volatile solids can be evaporated in a heated cell. Monochromatic VUV radiation ionizes the sample and both photoelectrons and photoions are velocity map imaged onto two fast position sensitive detectors and detected in delayed coincidence. High intensity synchrotron radiation leads to ionization rates above 10{sup 5} s{sup -1}. New data acquisition and processing approaches are discussed for recording coincidence processes at high rates. The setup is capable of resolving pulsed molecular beam profiles and the synchrotron time structure temporally. The latter is shown by photoelectron autocorrelation, which displays both the 1.04 MHz ring clock frequency as well as resolving the micro-pulses with a separation of 2 ns. Kinetic energy release analysis on the dissociative photoionization of CF{sub 4} indicates a dissociation mechanism change in the Franck-Condon allowed energy range of the first ion state.

  8. Dissociative double-photoionization of butadiene in the 25-45 eV energy range using 3-D multi-coincidence ion momentum imaging spectrometry

    NASA Astrophysics Data System (ADS)

    Oghbaie, Shabnam; Gisselbrecht, Mathieu; Laksman, Joakim; Mânsson, Erik P.; Sankari, Anna; Sorensen, Stacey L.

    2015-09-01

    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.

  9. Dissociative double-photoionization of butadiene in the 25-45 eV energy range using 3-D multi-coincidence ion momentum imaging spectrometry.

    PubMed

    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. PMID:26395707

  10. 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.

  11. 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.

  12. Double photoionization into double core-hole states in Xe.

    PubMed

    Hikosaka, Y; Lablanquie, P; Penent, F; Kaneyasu, T; Shigemasa, E; Eland, J H D; Aoto, T; Ito, K

    2007-05-01

    Double photoionization (DPI) leading to double core-hole states of Xe2+ 4d(-2) has been studied using a magnetic bottle time-of-flight spectrometer. The assignments of the Xe2+ 4d(-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 Xe2+ 4d(-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(-2) continuum with the 4p single photoionization, which is manifested in the relative intensities of the Xe2+ 4d(-2) components. PMID:17501570

  13. 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.

  14. DELICIOUS III: A multipurpose double imaging particle coincidence spectrometer for gas phase vacuum ultraviolet photodynamics studies

    NASA Astrophysics Data System (ADS)

    Garcia, G. A.; Cunha de Miranda, B. K.; Tia, M.; Daly, S.; Nahon, L.

    2013-05-01

    We present a versatile double imaging particle coincidence spectrometer operating in fully continuous mode, named DELICIOUS III, which combines a velocity map imaging device and a modified Wiley-McLaren time of flight momentum imaging analyzer for photoelectrons and photoions, respectively. The spectrometer is installed in a permanent endstation on the DESIRS vacuum ultraviolet (VUV) beamline at the French National Synchrotron Radiation Facility SOLEIL, and is dedicated to gas phase VUV spectroscopy, photoionization, and molecular dynamics studies. DELICIOUS III is capable of recording mass-selected threshold photoelectron photoion coincidence spectra with a sub-meV resolution, and the addition of a magnifying lens inside the electron drift tube provides a sizeable improvement of the electron threshold/ion mass resolution compromise. In fast electron mode the ultimate kinetic energy resolution has been measured at ΔE/E = 4%. The ion spectrometer offers a mass resolution—full separation of adjacent masses—of 250 amu for moderate extraction fields and the addition of an electrostatic lens in the second acceleration region allows measuring the full 3D velocity vector for a given mass with an ultimate energy resolution of ΔE/E = 15%, without sacrificing the mass resolution. Hence, photoelectron images are correlated both to the mass and to the ion kinetic energy and recoil direction, to access the electron spectroscopy of size-selected species, to study the photodissociation processes of state-selected cations in detail, or to measure in certain cases photoelectron angular distributions in the ion recoil frame. The performances of DELICIOUS III are explored through several examples including the photoionization of N2, NO, and CF3.

  15. Photoelectron spectroscopy of the nitrogen dimer (N2)2 and clusters (N2)n: N2 dimer revealed as the chromophore in photoionization of condensed nitrogen

    NASA Astrophysics Data System (ADS)

    Carnovale, Frank; Peel, J. Barrie; Rothwell, Richard G.

    1988-01-01

    The He i photoelectron spectra of gas-phase nitrogen dimer and nitrogen clusters have been measured in a pulsed cluster beam. The dimer (N2)2 is characterized by broad bands with vertical ionization energies which are 0.3±0.1 eV lower than for N2 monomer. The bands observed for a mixture of small clusters, estimated to be of average size N¯=10, are identical to the dimer bands except for further shifts of 0.3 eV to lower ionization energies. The clusters bandwidths and band shapes are virtually the same as measured for thin films of condensed N2, indicating that the nitrogen dimer (N2)2 is the ionization chromophore in each case. This offers support for Haberland's hypothesis that ionization of any Mn cluster produces the ion M+2Mn-2 provided M is a closed-shell atom or molecule. The theory of electronic relaxation polarization of the dielectric medium, which explains the gas-to-solid ionization energy shifts, is modified for the case of finite clusters and to account for dimer ion formation.

  16. Study of inner-shell vacancy cascades by coincidence techniques

    SciTech Connect

    LeBrun, T.; Arp, U.; MacDonald, M.; Southworth, S.H.

    1995-08-01

    An inner-shell vacancy in an atom decays by an intricate combination of Auger and fluorescence processes. The interrelation between these processes is not well understood because traditional studies of core-excited atoms focus on only one of the many particles that participate in the relaxation - largely ignoring the other components and the correlations between them. To understand these correlations we developed a coincidence technique that uses coincident detection of X-rays and electrons to select decay pathways that involve emission of both an X-ray photon and electrons. In the first application of this technique, the Ar 1s photoelectron spectrum was recorded selectively in coincidence with X-ray fluorescence to eliminate the asymmetric broadening and shifting of the energy distribution which results due to post-collision interaction with K-Auger electrons. This allowed the direct observation of the interaction between the photoelectron and the decay of core holes created after the initial photoionization event. We have also applied this technique to the much more complex problem of understanding Auger-electron spectra produced by vacancy cascades following inner-shell excitation. For example, we previously recorded non-coincident electron spectra of L{sub 2,3}MM Auger transitions following K-shell excitation of argon. Interpretation of these spectra is difficult because they are complicated and consist of many overlapping or unresolved Auger transitions between different ionic states.

  17. Fine- and hyperfine-structure effects in molecular photoionization. I. General theory and direct photoionization.

    PubMed

    Germann, Matthias; Willitsch, Stefan

    2016-07-28

    We develop a model for predicting fine- and hyperfine intensities in the direct photoionization of molecules based on the separability of electron and nuclear spin states from vibrational-electronic states. Using spherical tensor algebra, we derive highly symmetrized forms of the squared photoionization dipole matrix elements from which we derive the salient selection and propensity rules for fine- and hyperfine resolved photoionizing transitions. Our theoretical results are validated by the analysis of the fine-structure resolved photoelectron spectrum of O2 reported by Palm and Merkt [Phys. Rev. Lett. 81, 1385 (1998)] and are used for predicting hyperfine populations of molecular ions produced by photoionization. PMID:27475368

  18. Slow photoelectron spectroscopy of 3-hydroxyisoquinoline.

    PubMed

    Pan, Yi; Lau, Kai-Chung; Poisson, Lionel; Garcia, Gustavo A; Nahon, Laurent; Hochlaf, Majdi

    2013-08-29

    We studied the single photon ionization of gas phase 3-hydroxyisoquinoline by means of VUV synchrotron radiation coupled to a velocity map imaging electron/ion coincidence spectrometer. Near the ionization thresholds of 3-hydroxyisoquinoline, the photoionization is found to occur mainly via a direct process. The spectra are assigned with the help of theoretical calculations on the equilibrium geometries, electronic states patterns, harmonic and anharmonic wavenumbers of the lactim and lactam forms of 3-hydroxyisoquinoline and their cations. The slow photoelectron spectrum (SPES) of this lactim is dominated by vibrational transitions to the X̃ state of the cation. In addition, several weaker and complex bands are observed, corresponding to the population of the vibrational bands (pure or combination) of the à electronically excited state of the cation. The adiabatic ionization energy of 3-hydroxyisoquinoline and the lowest electronic state energetics of the lactim and lactam cationic forms are determined. PMID:23360492

  19. 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

  20. 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

  1. Photoionization of Benzophenone in the Gas Phase: Theory and Experiment.

    PubMed

    Khemiri, Noura; Messaoudi, Sabri; Abderrabba, Manef; Spighi, Gloria; Gaveau, Marc-André; Briant, Marc; Soep, Benoît; Mestdagh, Jean-Michel; Hochlaf, Majdi; Poisson, Lionel

    2015-06-11

    We report on the single photoionization of jet-cooled benzophenone using a tunable source of VUV synchrotron radiation coupled with a photoion/photoelectron coincidence acquisition device. The assignment and the interpretation of the spectra are based on a characterization by ab initio and density functional theory calculations of the geometry and of the electronic states of the cation. The absence of structures in the slow photoelectron spectrum is explained by a congestion of the spectrum due to the dense vibrational progressions of the very low frequency torsional mode in the cation either in pure form or in combination bands. Also a high density of electronic states has been found in the cation. Presently, we estimate the experimental adiabatic and vertical ionization energy of benzophenone at 8.80 ± 0.01 and 8.878 ± 0.005 eV, respectively. The ionization energy as well as the energies of the excited states are compared to the calculated ones. PMID:25866992

  2. Ar2 photoelectron spectroscopy mediated by autoionizing states.

    PubMed

    Briant, Marc; Poisson, Lionel; Hochlaf, Majdi; de Pujo, Patrick; Gaveau, Marc-André; Soep, Benoît

    2012-11-01

    This experimental work focuses on the complex autoionization dynamics of Ar(2) clusters below the first ionization energy of the argon atom. Ar(2) is submitted to vacuum ultraviolet radiation, and the photoelectron spectra are collected in coincidence with the cluster ions. The ionization dynamics is revealed by the dependence on the photon energy. We applied a new experimental method which we developed to analyze the photoelectron signal. Thus, we were able (i) to get the complete vibrational progression of Ar(2)(+) that was never observed up to now, especially identifying the 0-0 transition overcoming the usual Franck-Condon limitations during single photoionization, and (ii) to obtain the projections of the vibrational wave functions of the autoionizing states over the Ar(2)(+) functions. This method provides a powerful tool to test the potential energy curves computed by high level theoretical calculations on Rydberg states. PMID:23215381

  3. Photoelectron Spectroscopy of Doped Helium Nanodroplets

    SciTech Connect

    Loginov, Evgeniy; Rossi, Dominic; Drabbels, Marcel

    2005-10-14

    The photoionization dynamics of aniline doped helium droplets has been investigated by photoelectron spectroscopy. The photoelectron spectra resemble closely that of gas phase aniline, except for a droplet-size-dependent shift. This shift is caused by lowering of the ionization threshold upon solvation and can be readily estimated. The individual peaks in the photoelectron spectrum are broadened towards lower kinetic energy which is attributed to the relaxation of the photoelectrons as they pass through the helium droplet.

  4. 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.

  5. 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.

  6. 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.

  7. Synchrotron-based valence shell photoionization of CH radical.

    PubMed

    Gans, B; Holzmeier, F; Krüger, J; Falvo, C; Röder, A; Lopes, A; Garcia, G A; Fittschen, C; Loison, J-C; Alcaraz, C

    2016-05-28

    We report the first experimental observations of X(+) (1)Σ(+)←X (2)Π and a(+) (3)Π←X (2)Π single-photon ionization transitions of the CH radical performed on the DESIRS beamline at the SOLEIL synchrotron facility. The radical was produced by successive hydrogen-atom abstractions on methane by fluorine atoms in a continuous microwave discharge flow tube. Mass-selected ion yields and photoelectron spectra were recorded as a function of photon energy using a double imaging photoelectron/photoion coincidence spectrometer. The ion yield appears to be strongly affected by vibrational and electronic autoionizations, which allow the observation of high Rydberg states of the neutral species. The photoelectron spectra enable the first direct determinations of the adiabatic ionization potential and the energy of the first triplet state of the cation with respect to its singlet ground state. This work also brings valuable information on the complex electronic structure of the CH radical and its cation and adds new observations to complement our understanding of Rydberg states and autoionization processes. PMID:27250306

  8. Synchrotron-based valence shell photoionization of CH radical

    NASA Astrophysics Data System (ADS)

    Gans, B.; Holzmeier, F.; Krüger, J.; Falvo, C.; Röder, A.; Lopes, A.; Garcia, G. A.; Fittschen, C.; Loison, J.-C.; Alcaraz, C.

    2016-05-01

    We report the first experimental observations of X+ 1Σ+←X 2Π and a+ 3Π←X 2Π single-photon ionization transitions of the CH radical performed on the DESIRS beamline at the SOLEIL synchrotron facility. The radical was produced by successive hydrogen-atom abstractions on methane by fluorine atoms in a continuous microwave discharge flow tube. Mass-selected ion yields and photoelectron spectra were recorded as a function of photon energy using a double imaging photoelectron/photoion coincidence spectrometer. The ion yield appears to be strongly affected by vibrational and electronic autoionizations, which allow the observation of high Rydberg states of the neutral species. The photoelectron spectra enable the first direct determinations of the adiabatic ionization potential and the energy of the first triplet state of the cation with respect to its singlet ground state. This work also brings valuable information on the complex electronic structure of the CH radical and its cation and adds new observations to complement our understanding of Rydberg states and autoionization processes.

  9. Near-Edge X-Ray Absorption Fine Structures Revealed in Core Ionization Photoelectron Spectroscopy

    NASA Astrophysics Data System (ADS)

    Nakano, M.; Selles, P.; Lablanquie, P.; Hikosaka, Y.; Penent, F.; Shigemasa, E.; Ito, K.; Carniato, S.

    2013-09-01

    Simultaneous core ionization and core excitation have been observed in the C2H2n (n=1, 2, 3) molecular series using synchrotron radiation and a magnetic bottle time-of-flight electron spectrometer. Rich satellite patterns corresponding to (K-2V) core excited states of the K-1 molecular ions have been identified by detecting in coincidence the photoelectron with the two Auger electrons resulting from the double core hole relaxation. A theoretical model is proposed providing absolute photoionization cross sections and revealing clear signatures of direct (monopolar) and conjugate (dipolar near-edge x-ray absorption fine structure) shakeup lines of comparable magnitude.

  10. Near-edge x-ray absorption fine structures revealed in core ionization photoelectron spectroscopy.

    PubMed

    Nakano, M; Selles, P; Lablanquie, P; Hikosaka, Y; Penent, F; Shigemasa, E; Ito, K; Carniato, S

    2013-09-20

    Simultaneous core ionization and core excitation have been observed in the C(2)H(2n) (n=1, 2, 3) molecular series using synchrotron radiation and a magnetic bottle time-of-flight electron spectrometer. Rich satellite patterns corresponding to (K(-2)V) core excited states of the K(-1) molecular ions have been identified by detecting in coincidence the photoelectron with the two Auger electrons resulting from the double core hole relaxation. A theoretical model is proposed providing absolute photoionization cross sections and revealing clear signatures of direct (monopolar) and conjugate (dipolar near-edge x-ray absorption fine structure) shakeup lines of comparable magnitude. PMID:24093255

  11. Ultraviolet photoionization in CO2 TEA lasers

    NASA Astrophysics Data System (ADS)

    Scott, S. J.; Smith, A. L. S.

    1988-07-01

    The effects of gas composition and spark parameters on the UV emission in CO2 TEA laser gas mixtures were investigated together with the nature of photoionization process and the photoelectron-loss mechanism. A linear relationship was found between N2 concentration and photoionization (with no such dependence on C concentration, from CO and CO2), but the increases in photoionization that could be effected by optimizing the spark discharge circuit parameters were much higher than those produced by changes in gas composition. UV emission was directly proportional to the amount of stored electrical energy in the spark-discharge circuit and to the cube of the peak current produced in the spark by the discharge of this energy. Photoionization was also found to be proportional to the spark electrode gap. It was found that free-space sparks gave a considerably broader emission pattern than a surface-guided notched spark.

  12. Effects of dimerization on the photoelectron angular distribution parameters from chiral camphor enantiomers obtained with circularly polarized vacuum-ultraviolet radiation

    SciTech Connect

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

    2010-09-15

    As an intermediate state of matter between the free monomeric gas phase and the solid state, clusters may exhibit a specific electronic structure and photoionization dynamics that can be unraveled by different types of electron spectroscopies. From mass-selected ion yield scans measured for photoionization of (R)-camphor, the ionization potentials (IPs) of the monomer (8.66{+-}0.01 eV), and of the homochiral dimer ({<=}8.37{+-}0.01 eV) and trimer ({<=}8.30{+-}0.01 eV) were obtained. These spectra, combined with threshold photoelectron spectroscopy and velocity map ion imaging, allow us to show that the camphor monomer and dimer photoionization channels are decoupled, i.e., that the highest occupied molecular orbital (HOMO) of the dimer does not undergo a dissociative ionization process that would lead to a spurious contribution to the monomer ion channel. Therefore mass selection, as achieved in our imaging photoelectron-photoion coincidence experiments, leads to size selection of the nascent monomer or dimer species. Since both the monomer and dimer are chiral, their photoelectron angular distribution (PAD) not only involves the usual {beta} anisotropy parameter but also a chiral asymmetry parameter b{sub 1} that can generate a forward-backward asymmetry in the PAD. This has been investigated using circularly polarized light (CPL) to record the photoelectron circular dichroism (PECD) in the near-threshold vacuum-ultraviolet (VUV) photoionization region. Analysis of size-selected electron images recorded with left- and right-handed CPL shows that over the first 1.5 eV above the HOMO orbital ionization potentials (IPs), the {beta} parameter is not affected by the dimerization process, while the chiral b{sub 1} parameter shows clear differences between the monomer and the dimer, confirming that PECD is a subtle long-range probe of the molecular potential.

  13. Effects of dimerization on the photoelectron angular distribution parameters from chiral camphor enantiomers obtained with circularly polarized vacuum-ultraviolet radiation

    NASA Astrophysics Data System (ADS)

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

    2010-09-01

    As an intermediate state of matter between the free monomeric gas phase and the solid state, clusters may exhibit a specific electronic structure and photoionization dynamics that can be unraveled by different types of electron spectroscopies. From mass-selected ion yield scans measured for photoionization of (R)-camphor, the ionization potentials (IPs) of the monomer (8.66±0.01 eV), and of the homochiral dimer (⩽8.37±0.01 eV) and trimer (⩽8.30±0.01 eV) were obtained. These spectra, combined with threshold photoelectron spectroscopy and velocity map ion imaging, allow us to show that the camphor monomer and dimer photoionization channels are decoupled, i.e., that the highest occupied molecular orbital (HOMO) of the dimer does not undergo a dissociative ionization process that would lead to a spurious contribution to the monomer ion channel. Therefore mass selection, as achieved in our imaging photoelectron-photoion coincidence experiments, leads to size selection of the nascent monomer or dimer species. Since both the monomer and dimer are chiral, their photoelectron angular distribution (PAD) not only involves the usual β anisotropy parameter but also a chiral asymmetry parameter b1 that can generate a forward-backward asymmetry in the PAD. This has been investigated using circularly polarized light (CPL) to record the photoelectron circular dichroism (PECD) in the near-threshold vacuum-ultraviolet (VUV) photoionization region. Analysis of size-selected electron images recorded with left- and right-handed CPL shows that over the first 1.5 eV above the HOMO orbital ionization potentials (IPs), the β parameter is not affected by the dimerization process, while the chiral b1 parameter shows clear differences between the monomer and the dimer, confirming that PECD is a subtle long-range probe of the molecular potential.

  14. Imaging molecular orbitals using photoionization

    NASA Astrophysics Data System (ADS)

    Santra, Robin

    2006-10-01

    The interpretation of a recent experiment using high-order harmonic generation [Itatani et al., Nature 432 (2004) 867] as a measurement of the highest occupied molecular orbital of a molecule is conceptually problematic, even if the independent-particle picture is taken seriously. Guided by the relationship between the amplitude for one-photon-induced electron emission and the electron-ion recombination amplitude in the three-step model of high-order harmonic generation, it is argued that synchrotron-based photoionization might be a superior approach to imaging molecular orbitals. Within the Hartree-Fock independent-particle picture, the molecular-frame photoelectron angular distributions, measured as a function of photon energy, could be used to reconstruct all orbitals occupied in the Hartree-Fock ground state of the molecule investigated. It is suggested that laser alignment techniques could be employed to facilitate the measurement of the molecular-frame photoelectron angular distributions.

  15. 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.

  16. Attosecond Delays in Molecular Photoionization.

    PubMed

    Huppert, Martin; Jordan, Inga; Baykusheva, Denitsa; von Conta, Aaron; Wörner, Hans Jakob

    2016-08-26

    We report measurements of energy-dependent photoionization delays between the two outermost valence shells of N_{2}O and H_{2}O. The combination of single-shot signal referencing with the use of different metal foils to filter the attosecond pulse train enables us to extract delays from congested spectra. Remarkably large delays up to 160 as are observed in N_{2}O, whereas the delays in H_{2}O are all smaller than 50 as in the photon-energy range of 20-40 eV. These results are interpreted by developing a theory of molecular photoionization delays. The long delays measured in N_{2}O are shown to reflect the population of molecular shape resonances that trap the photoelectron for a duration of up to ∼110 as. The unstructured continua of H_{2}O result in much smaller delays at the same photon energies. Our experimental and theoretical methods make the study of molecular attosecond photoionization dynamics accessible. PMID:27610849

  17. Is CO Carbon KVV Auger Electron Emission Affected by the Photoelectron?

    SciTech Connect

    Pruemper, G.; Fukuzawa, H.; Sakai, K.; Ueda, K.; Rolles, D.; Prince, K. C.; Harries, J. R.; Tamenori, Y.; Berrah, N.

    2008-12-05

    Angular distributions (ADs) of O{sup +} fragments from C 1s photoexcited CO detected in coincidence with carbon KVV Auger electrons emitted in the horizontal direction were measured at photon energies of 298, 305, 320, and 450 eV. At 450 eV, the ADs are polarization-independent and coincide with the molecular-frame Auger electron angular distribution. All measured ADs can be rationalized as a product of the same molecular-frame Auger electron angular distribution and the axial selectivity in the photoionization process. Thus the interaction between the photoelectron and the Auger electron for the normal Auger decay of CO can be neglected, and the two-step model is a good approximation.

  18. Near threshold studies of photoelectron satellites

    SciTech Connect

    Heimann, P.A.

    1986-11-01

    Photoelectron spectroscopy and synchrotron radiation have been used to study correlation effects in the rare gases: He, Ne, Ar, Kr, and Xe. Two kinds of time-of-flight electron analyzers were employed to examine photoionization very close to threshold and at higher kinetic energies. Partial cross sections and angular distributions have been measured for a number of photoelectron satellites. The shake-off probability has been determined at some inner-shell resonances. 121 refs., 28 figs., 13 tabs.

  19. Shape resonant features in the photoionization spectra of NO

    SciTech Connect

    Wallace, Scott; Dill, Dan; Dehmer, Joseph L.

    1982-01-01

    Calculations of core and valence level photoionization spectra of NO are presented and compared with available experimental data. A low-lying continuum shape resonance is identified in the sigma photoionization channel, which is the analog of similar states found in other first-row diatomic molecules. Both partial cross sections and photoelectron angular distributions are discussed, and the effect of nuclear motion on these observables is treated.

  20. Photoionization from excited states of helium

    NASA Technical Reports Server (NTRS)

    Jacobs, V. L.

    1973-01-01

    The cross sections for photoionization from the 2 1S, 2 3S, 2 1P and 2 3P excited states of helium are calculated for photoelectron energies below the n = 2 threshold of He(+) using Hylleraas bound state wave functions and 1s-2s-2p close coupling final state wave functions. The resonant structures associated with the lowest-lying 1S, 1P, 3P, and 1D autoionizing states of helium are found to be characterized by large values of the line profile parameter q. The cross sections and the photoelectron angular distribution asymmetry parameters for the P-states are calculated for various polarization states of the target atom and the incident photon. Experiments which would lead to the separate determinations of the S- and D- wave partial photoionization cross sections are discussed.

  1. Time-dependent photoelectron angular distributions

    NASA Astrophysics Data System (ADS)

    Wang, Xiangyang

    1999-09-01

    I show that the angular distribution of electrons photoionized from gas phase targets by short light pulses is time-dependent, when the orbital momentum composition of the photocurrent changes with excitation energy so evolves with the time of detection. A theory of time- dependent photoionization is outlined and general formulas of time-dependent photoelectron flux and angular distribution are given. Two general propagator methods suitable to describe the time-dependent photoionization and scattering processes are developed. The photoionization process is viewed as a local excitation followed by a half scattering. The local excitation process is solved theoretically in a small region around the target core. This approach has been generalized to describe the evolution of a wavepacket in an unbound system. An asymptotic propagator theorem is discovered and used to derive analytic expressions for asymptotic propagators. The origin of the time dependence is explored by parameterizing the time delay and orbital momentum coupling in a two channel model. K-shell photoionization of N2 and CO are calculated with this time- dependent photoionization theory, implemented using a multiple scattering model. Numerical results demonstrate that the time dependence of photoelectron angular distributions is a realistic effect.

  2. Photoelectron Spectra

    ERIC Educational Resources Information Center

    Bock, Hans; Mollere, Phillip D.

    1974-01-01

    Presents an experimental approach to teaching molecular orbital models. Suggests utilizing photoelectron spectroscopy and molecular orbital theory as complementary approaches to teaching the qualitative concepts basic to molecular orbital theory. (SLH)

  3. Photoionization Dynamics in Pure Helium Droplets

    SciTech Connect

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

    2007-02-04

    The photoionization and photoelectron spectroscopy of pure He droplets are investigated at photon energies between 24.6 eV (the ionization energy of He) and 28 eV. Time-of-flight mass spectra and photoelectron images were obtained at a series of molecular beam source temperatures and pressures to assess the effect of droplet size on the photoionization dynamics. At source temperatures below 16 K, the photoelectron images are dominated by fast electrons produced via direct ionization of He atoms, with a small contribution from very slow electrons with kinetic energies below 1 meV arising from an indirect mechanism. The fast photoelectrons have as much as 0.5 eV more kinetic energy than those from atomic He at the same photon energy. This result is interpreted and simulated within the context of a 'dimer model', in which one assumes vertical ionization from two nearest neighbor He atoms to the attractive region of the He2+ potential energy curve. Possible mechanism for the slow electrons, which were also seen at energies below IE(He), are discussed, including vibrational autoionizaton of Rydberg states comprising an electron weakly bound to the surface of a large HeN+ core.

  4. Atomic photoelectron-spectroscopy studies using synchrotron radiation

    SciTech Connect

    Kobrin, P.H.

    1983-02-01

    Photoelectron spectroscopy combined with tunable synchrotron radiation has been used to study the photoionization process in several atomic systems. The time structure of the synchrotron radiation source at the Stanford Synchrotron Radiation Laboratory (SSRL) was used to record time-of-flight (TOF) photoelectron spectra of gaseous Cd, Hg, Ne, Ar, Ba, and Mn. The use of two TOF analyzers made possible the measurement of photoelectron angular distributions as well as branching ratios and partial cross sections.

  5. Vacuum upgrade and enhanced performances of the double imaging electron/ion coincidence end-station at the vacuum ultraviolet beamline DESIRS

    NASA Astrophysics Data System (ADS)

    Tang, Xiaofeng; Garcia, Gustavo A.; Gil, Jean-François; Nahon, Laurent

    2015-12-01

    We report here the recent upgrade of the SAPHIRS permanent photoionization end-station at the DESIRS vacuum ultraviolet beamline of synchrotron SOLEIL, whose performances have been enhanced by installing an additional double-skimmer differential chamber. The smaller molecular beam profile obtained at the interaction region has increased the mass resolution of the double imaging photoelectron photoion coincidence (i2PEPICO) spectrometer, DELICIOUS III, installed in the photoionization chamber of the SAPHIRS endstation, by a factor of two, to M/ΔM ˜ 1700 (FWHM). The electron kinetic energy resolution offered by the velocity map imaging (VMI) part of the spectrometer has been improved down to 2.8% (ΔE/E) as we show on the N2 photoionization case in the double skimmer configuration. As a representative example of the overall state-of-the-art i2PEPICO performances, experimental results of the dissociation of state-selected O2+ (B 2 ∑ g - , v+ = 0-6) molecular ions performed at the fixed photon energy of hν = 21.1 eV are presented.

  6. Vacuum upgrade and enhanced performances of the double imaging electron/ion coincidence end-station at the vacuum ultraviolet beamline DESIRS.

    PubMed

    Tang, Xiaofeng; Garcia, Gustavo A; Gil, Jean-François; Nahon, Laurent

    2015-12-01

    We report here the recent upgrade of the SAPHIRS permanent photoionization end-station at the DESIRS vacuum ultraviolet beamline of synchrotron SOLEIL, whose performances have been enhanced by installing an additional double-skimmer differential chamber. The smaller molecular beam profile obtained at the interaction region has increased the mass resolution of the double imaging photoelectron photoion coincidence (i(2)PEPICO) spectrometer, DELICIOUS III, installed in the photoionization chamber of the SAPHIRS endstation, by a factor of two, to M/ΔM ∼ 1700 (FWHM). The electron kinetic energy resolution offered by the velocity map imaging (VMI) part of the spectrometer has been improved down to 2.8% (ΔE/E) as we show on the N2 photoionization case in the double skimmer configuration. As a representative example of the overall state-of-the-art i(2)PEPICO performances, experimental results of the dissociation of state-selected O2(+)(B(2)∑(g)(-), v(+) = 0-6) molecular ions performed at the fixed photon energy of hν = 21.1 eV are presented. PMID:26724007

  7. O1s photoionization dynamics in oriented NO2

    NASA Astrophysics Data System (ADS)

    Stener, Mauro; Decleva, Piero; Yamazaki, Masakazu; Adachi, Jun-ichi; Yagishita, Akira

    2011-05-01

    We have performed extensive density functional theory (DFT) calculations, partial cross sections, dipole prepared continuum orbitals, dipole amplitudes and phase shifts, asymmetry parameters β, and molecular frame photoelectron angular distributions, to elucidate the O1s photoionization dynamics of NO2 molecule with emphasis on the shape resonances in the O1s ionization continuum. In the shape resonance region, the β parameters and photoelectron angular distributions have been compared with our experimental results. Fairly good agreement between the theory and experiment has confirmed that the DFT level calculations can well describe the photoionization dynamics of the simple molecule such as NO2. Interference due to equivalent atom photoionization is theoretically considered, and the possibility of detection of the effect in the two degenerate channels with different combinations of light polarization and photoemission direction is discussed.

  8. 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.

  9. 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.

  10. Vacuum ultraviolet photoelectron spectroscopy of atoms and molecules

    NASA Technical Reports Server (NTRS)

    Samson, J. A. R.

    1978-01-01

    For a complete study of the photoionization of atoms and molecules it is essential to make use of the technique of Photoelectron Spectroscopy and the continuum characteristics of synchrotron radiation. A brief review is given of the application of the above techniques in measuring partial photoionization cross sections and the angular distribution assymetry parameter beta. Selected results are given, which are compared to theoretical values.

  11. Molecular photoionization dynamics

    SciTech Connect

    Dehmer, Joseph L.

    1982-05-01

    This program seeks to develop both physical insight and quantitative characterization of molecular photoionization processes. Progress is briefly described, and some publications resulting from the research are listed. (WHK)

  12. 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.

  13. 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.

  14. 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.

  15. Nondipole Photoionization Parameters of Atomic Mercury

    NASA Astrophysics Data System (ADS)

    Banerjee, T.; Manson, S. T.

    2005-05-01

    Over the past few years, photoionization parameters have been found to be affected by nondipole terms at much lower energies than was known earlier [1,2]. The primary motivation for the present investigation is to study the effect of interchannel coupling involving E1 and E2 photoionization channels from subshells with large orbital angular momentum (l>2). In an extension of earlier work [3], the nondipole photoelectron angular distribution asymmetry parameters γandδ from the 6s and 5d subshells of atomic mercury have been obtained in the energy range from the respective thresholds up to 45 au. Relativistic-Random-Phase Approximation (RRPA) theory at various levels of truncation of the RRPA was used which allowed us to pinpoint the effects of interchannel coupling. The role of interchannel coupling between the 6s and 5d photoionization channels and the 4f channels in both the dipole (E1) and the quadrupole (E2) manifolds has been detailed and has been found to be of considerable significance. This work was supported by DST and NSF. [1] A. Derevianko, W. R. Johnson and K. T. Cheng , At. Data Nucl. Data Tables 73, 153 (1999). [2] O. Hemmers, et al, Phys. Rev. Lett. 91, 053002 (2003); 93, 11301 (2004). [3] P. C. Deshmukh, Radiation Phys. and Chem. 70, 515 (2004) and references therein.

  16. Asymmetric photoelectron momentum distribution driven by two-color XUV fields

    NASA Astrophysics Data System (ADS)

    Wu, Wan-Yang; He, Feng

    2016-02-01

    The photoionization of He+ in two-color XUV fields is studied by numerically solving the time-dependent Schrödinger equation. He+ may be ionized by directly absorbing one high-energetic photon or by absorbing two photons sequentially by mediating an excited state. The interference of these two pathways results in either enhancement or suppression of photoionization, depending on the propagating direction of the photoelectron and the relative phase of two pulses. The two-pathway interference also induces the split of photoelectron momenta. This study shows that the participation of intermediate states may substantially change photoionization processes.

  17. Quantum optimal control of photoelectron spectra and angular distributions

    NASA Astrophysics Data System (ADS)

    Goetz, R. Esteban; Karamatskou, Antonia; Santra, Robin; Koch, Christiane P.

    2016-01-01

    Photoelectron spectra and photoelectron angular distributions obtained in photoionization reveal important information on, e.g., charge transfer or hole coherence in the parent ion. Here we show that optimal control of the underlying quantum dynamics can be used to enhance desired features in the photoelectron spectra and angular distributions. To this end, we combine Krotov's method for optimal control theory with the time-dependent configuration interaction singles formalism and a splitting approach to calculate photoelectron spectra and angular distributions. The optimization target can account for specific desired properties in the photoelectron angular distribution alone, in the photoelectron spectrum, or in both. We demonstrate the method for hydrogen and then apply it to argon under strong XUV radiation, maximizing the difference of emission into the upper and lower hemispheres, in order to realize directed electron emission in the XUV regime.

  18. Photoionization by an ultraintense laser field: Response of atomic xenon

    SciTech Connect

    DiChiara, A. D.; Ghebregziabher, I.; Waesche, J. M.; Stanev, T.; Ekanayake, N.; Barclay, L. R.; Wells, S. J.; Watts, A.; Videtto, M.; Mancuso, C. A.; Walker, B. C.

    2010-04-15

    We present energy- and angle-resolved photoionization from Xe in an ultrastrong laser field at 10{sup 19} W/cm{sup 2}. The observed yields are consistent with the tunneling ionization of Xe{sup 9+} to Xe{sup 24+}. However, energy and angle-resolved photoelectron spectra show differences for electrons whose final energies are above or below 0.5 MeV, which is approximately the ponderomotive energy at these intensities. Above 0.5 MeV, the observed photoelectron cutoff energy (between 1 and 1.35 MeV), photoelectron energy spectra, and the angle-resolved photoelectron azimuthal distributions agree with a model using tunneling ionization, multiple charge states, a classical relativistic continuum, and nonparaxial three-dimensional (3D) focused laser field. Below 0.5 MeV the yields and angular distributions observed indicate dynamics not included within a classical, single electron model of the interaction.

  19. Rotamers and Migration: Investigating the Dissociative Photoionization of Ethylenediamine.

    PubMed

    Muller, Giel; Voronova, Krisztina; Sztáray, Bálint; Meloni, Giovanni

    2016-06-01

    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. PMID:27177327

  20. Post-collision-interaction distortion of low-energy photoelectron spectra associated with double Auger decay

    SciTech Connect

    Gerchikov, L.; Sheinerman, S.

    2011-08-15

    Atomic inner-shell photoionization followed by double Auger decay is investigated. The focus of our study is the effect of post-collision interaction (PCI) on the photoelectron energy distribution. A semi-classical approach is employed to describe the PCI distortion of the photoelectron line shapes associated with both direct and cascade double Auger decays. This approach is shown to be valid at low photoelectron energies, whereas for large incident photon energies it reduces to the eikonal approximation. The theory is applied to the case of Ar 2p photoionization spectra and good agreement with available experimental data is achieved.

  1. Angular correlation between photoelectrons and auger electrons from K-shell ionization of neon.

    PubMed

    Landers, A L; Robicheaux, F; Jahnke, T; Schöffler, M; Osipov, T; Titze, J; Lee, S Y; Adaniya, H; Hertlein, M; Ranitovic, P; Bocharova, I; Akoury, D; Bhandary, A; Weber, Th; Prior, M H; Cocke, C L; Dörner, R; Belkacem, A

    2009-06-01

    We have used cold target recoil ion momentum spectroscopy to study the continuum correlation between the photoelectron of core-photoionized neon and the subsequent Auger electron. We observe a strong angular correlation between the two electrons. Classical trajectory Monte Carlo calculations agree quite well with the photoelectron energy distribution that is shifted due to the potential change associated with Auger decay. However, a striking discrepancy results in the distribution of the relative angle between Auger and photoelectron. The classical model predicts a shift in photoelectron flux away from the Auger emission direction, and the data strikingly reveal that the flux is lost rather than diverted, indicating that the two-step interpretation of photoionization followed by Auger emission is insufficient to fully describe the core-photoionization process. PMID:19658860

  2. Angular Correlation between Photoelectrons and Auger Electrons from K-Shell Ionization of Neon

    SciTech Connect

    Landers, A. L.; Robicheaux, F.; Bhandary, A.; Jahnke, T.; Schoeffler, M.; Titze, J.; Akoury, D.; Doerner, R.; Osipov, T.; Lee, S. Y.; Adaniya, H.; Hertlein, M.; Weber, Th.; Prior, M. H.; Belkacem, A.; Ranitovic, P.; Bocharova, I.; Cocke, C. L.

    2009-06-05

    We have used cold target recoil ion momentum spectroscopy to study the continuum correlation between the photoelectron of core-photoionized neon and the subsequent Auger electron. We observe a strong angular correlation between the two electrons. Classical trajectory Monte Carlo calculations agree quite well with the photoelectron energy distribution that is shifted due to the potential change associated with Auger decay. However, a striking discrepancy results in the distribution of the relative angle between Auger and photoelectron. The classical model predicts a shift in photoelectron flux away from the Auger emission direction, and the data strikingly reveal that the flux is lost rather than diverted, indicating that the two-step interpretation of photoionization followed by Auger emission is insufficient to fully describe the core-photoionization process.

  3. Energetic photoelectrons and the polar rain

    NASA Technical Reports Server (NTRS)

    Decker, Dwight T.; Jasperse, J. R.; Winningham, J. D.

    1990-01-01

    In the daytime midlatitudes, the Low Altitude Plasma Instrument (LAPI) on board the Dynamics Explorer 2 satellite has observed photoelectrons with energies as high as 850 eV. These energetic photoelectrons are an extension of the 'classical' photoelectrons (less than 60 eV) and result from photoionization of neutrals by soft solar X-rays. Since these photoelectrons are produced wherever the solar flux is incident on the earth's atmosphere, they should be present in sunlit polar cap. But in the polar cap, over these same energies, there is a well-known electron population: the polar rain, a low intensity electron flux of magnetospheric origin. Thus, in the sunlit polar cap, an energetic population of electrons should consist of both an ionospheric (photoelectron) and a magnetospheric (polar rain) component. Using numerical solutions of an electron transport equation with appropriate boundary conditions and sunlit polar cap LAPI data, it is shown that the two populations (photoelectron and polar rain) are indeed present and are both needed to explain polar cap observations.

  4. Photoionization of Li2

    NASA Astrophysics Data System (ADS)

    Li, Y.; Pindzola, M. S.; Ballance, C. P.; Colgan, J.

    2014-05-01

    Single and double photoionization cross sections for Li2 are calculated using a time-dependent close-coupling method. The correlation between the outer two electrons of Li2 is obtained by relaxation of the close-coupled equations in imaginary time. Propagation of the close-coupled equations in real time yields single and double photoionization cross sections for Li2. The two active electron cross sections are compared with one active electron distorted-wave and close-coupling results for both Li and Li2. This work was supported in part by grants from NSF and US DoE. Computational work was carried out at NERSC in Oakland, California, NICS in Knoxville, Tennessee, and OLCF in Oak Ridge, Tennessee.

  5. Photoionization of argon clusters

    SciTech Connect

    Dehmer, Patricia M.; Pratt, Stephen T.

    1982-01-01

    Argon clusters were produced in a free supersonic molecular beam expansion of pure argon at room temperature and the photoionization efficiency curves of the trimer through hexamer were measured in the wavelength regions from threshold to 700 Â. A study of the Ar⁺3 photoionization efficiency curve as a function of nozzle stagnation pressure shows that fragmentation of heavier clusters can dominate the spectrum, even near threshold, and even when the nozzle conditions are such that the Ar⁺4 intensity is only a small fraction of the Ar⁺3 intensity. The Ar⁺3 photoionization efficiency curve, obtained using nozzle stagnation conditions such that no heavier ions were detected, exhibits several broad peaks near threshold which show similarities to bands of the dimer. At high nozzle stagnation pressures, the photoionization efficiency curves for Ar⁺3 to Ar⁺6 are nearly identical due to the effects of fragmentation. These spectra exhibit two very broad features which are similar to features observed in the solid. The threshold regions for all the positive ions show extremely gradual onsets, making it difficult to determine the appearance potentials accurately. The appearance potentials for Ar⁺2 and Ar⁺3 are 855.0±1.5 and 865.0±1.5 Â, respectively, yielding a value of 0.18±0.05 eV for the dissociation energy of Ar⁺3. The appearance potentials for the heavier clusters Ar⁺4 through Ar⁺6 are all approximately 870±2 Â.

  6. Photoionization of Li

    NASA Astrophysics Data System (ADS)

    Colgan, James

    2011-05-01

    The time-dependent close-coupling approach to multiple photoionization of lithium is presented. Double photoionization of lithium can be treated as a two-electron ejection process where the outgoing electrons move in the field of a ``frozen-core'' Li2+ 1 s state. Recent calculations of this process have resulted in total and triple differential cross sections that are in good agreement with other close-coupling approaches. The time-dependent approach can also be extended to treat the interaction of all three lithium electrons, as is required if triple photoionization is examined, that is, the simultaneous ejection of all three electrons from lithium. The most detailed information about this process is found in the fully angular and energy differential cross sections, which provide information as to how the ionized electrons leave the atom. We present our formulation of the fully differential cross section expression, and provide some convergence studies of the angular distributions. The Los Alamos National Laboratory is operated by Los Alamos National Security, LLC for the National Nuclear Security Administration of the U.S. Department of Energy under Contract No. DE-AC5206NA25396.

  7. 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.

  8. Photoabsorption and photoionization of chlorine dioxide

    SciTech Connect

    Flesch, R.; Ruehl, E.; Hottmann, K.; Baumgaertel, H. )

    1993-01-28

    Photoprocesses of chlorine dioxide in the near-UV have become highly important for stratospheric photoprocesses at high latitudes, especially in Antarctica. Chlorine dioxide has been identified among other absorbers because of its specific absorption cross section in the near-UV. Possible contributions of chlorine dioxide photochemistry to polar ozone depletion have been discussed recently. The high-resolution He I photoelectron spectrum and the absolute (vacuum-UV) absorption cross section (6-25 eV) as well as the ionic fragmentation of chlorine dioxide (OCIO) are reported. The photoelectron spectrum is interpreted in terms of exchange splitting effects of the various singlet and triplet cation states as well as by comparison to chemically related molecules. The vacuum-UV absorption spectrum shows different Rydberg series converging to the cation states. These Rydberg series and their vibrational progressions are assigned by term value arguments, dipole selection rules, and comparison with the photoelectron spectrum. Photoionization mass spectrometry is used for measurements of the ionization and fragmentation threshold of OCIO. The major fragment is ClO[sup +] which occurs above 13.4 eV. Thermomechanical data such as heats of formation and bond dissociation energies are derived. No evidence for isomerization of OClO[sup +] is found, as observed for the electronically excited neutral molecule. 54 refs., 6 figs., 7 tabs.

  9. Autoionization of OCS by threshold photoelectron spectroscopy

    NASA Astrophysics Data System (ADS)

    Delwiche, Jacques; Hubin-Franskin, Marie-Jeanne; Guyon, Paul-Marie; Nenner, Irène

    1981-04-01

    Autoionization of carbonyl sulfide between 12 and 16 eV has been investigated by photoionization using the pulsed synchrotron radiation from ACO Orsay's storage ring. The threshold photoelectron spectrum and the total photoionization spectrum of carbonyl sulfide have been recorded at high resolution in the wavelength range between 112.0 and 65.0 nm (11-19 eV). Threshold energy electrons are observed in specific wavelength regions: (i) at excitation energies where the X˜, Ã, B˜, and C˜ ionic states are formed by a direct process; (ii) in the à state region where resonant autoionization to à can be understood classically within the Franck-Condon approximation; (iii) in the ÖX˜ Franck-Condon gap between 90 and 110 nm, where resonant autoionization leads to very sharp electron energy distribution strongly peaked at zero energy. Here the mechanism must be more complex.

  10. Theoretical and Experimental Photoelectron Spectroscopy Characterization of the Ground State of Thymine Cation.

    PubMed

    Majdi, Youssef; Hochlaf, Majdi; Pan, Yi; Lau, Kai-Chung; Poisson, Lionel; Garcia, Gustavo A; Nahon, Laurent; Al-Mogren, Muneerah Mogren; Schwell, Martin

    2015-06-11

    We report on the vibronic structure of the ground state X̃(2)A″ of the thymine cation, which has been measured using a threshold photoelectron photoion coincidence technique and vacuum ultraviolet synchrotron radiation. The threshold photoelectron spectrum, recorded over ∼0.7 eV above the ionization potential (i.e., covering the whole ground state of the cation) shows rich vibrational structure that has been assigned with the help of calculated anharmonic modes of the ground electronic cation state at the PBE0/aug-cc-pVDZ level of theory. The adiabatic ionization energy has been experimentally determined as AIE = 8.913 ± 0.005 eV, in very good agreement with previous high resolution results. The corresponding theoretical value of AIE = 8.917 eV has been calculated in this work with the explicitly correlated method/basis set (R)CCSD(T)-F12/cc-pVTZ-F12, which validates the theoretical approach and benchmarks its accuracy for future studies of medium-sized biological molecules. PMID:25539153

  11. Photoionization and electron-ion recombination of Ti I

    NASA Astrophysics Data System (ADS)

    Nahar, Sultana N.

    2016-07-01

    Study of the inverse processes of photoionization and electron-ion recombination of (Ti I + h ν ⇋ Ti II + e) using the unified method is reported. The method, based on close coupling (CC) approximation and R-matrix method, subsumes both the radiative recombination (RR) and dielectronic recombination (DR) in a unified manner and provides state-specific and total electron-ion recombination rate coefficients which are self-consistent with the state-specific photoionization cross sections. The present results include state-specific electron-ion recombination rates (αRC(i))and partial photoionization cross sections (σPI(i)) leaving the ion in the ground state of 813 bound states with n ≤ 10 and l ≤ 9 of Ti I. Various features of state-specific and total electron-ion recombination with temperature, and the corresponding photoionization cross sections with energies are discussed with illustrations. Due to closely lying excited states near the ground state of the core, photoionization cross sections show presence of narrow Rydberg resonances in low energy region near the ionization threshold. Many excited states also show broad and enhanced Seaton resonances due to PEC (photo-excitation-of-core) which contribute to the high temperature recombination. The total recombination rate coefficient is found to show a low hump around temperature 280 K and a high dielectronic recombination peak at temperature 25,000 K. Total spectrum of recombination cross sections and rates with photoelectron energy are also presented for experimental observation. Calculations were carried out using a CC wave function expansion of 36 states of the core ion Ti II. The large set of data for recombination rates and partial photoionization cross sections with resonances should provide a complete and accurate modelings of plasmas.

  12. Photoionization cross sections and oscillator strengths of neutral cesium

    NASA Astrophysics Data System (ADS)

    Haq, S. U.; Nadeem, Ali; Nawaz, M.

    2012-11-01

    The absolute photoionization cross sections from the 6p 2P1/2 excited state of cesium at threshold and above the threshold region have been measured using the saturation absorption technique. The photoionization cross section at the ionization threshold is determined as 22.6±3.6 Mb, whereas in the region above threshold its value ranges from 22 to 20 Mb for photoelectron energies up to 0.1 eV. A comparison of the photoionization cross sections with earlier reported theoretical and experimental data have been presented and are in good agreement within the uncertainty. In addition, the oscillator strengths of the 6p 2P1/2→n d 2D3/2 (21≤n≤60) Rydberg transitions of cesium have been calibrated using the threshold value of the photoionization cross section. A complete picture of the oscillator strengths from the present work and previously reported data from n=5-60 is presented.

  13. Photoionization of Atomic Sc

    NASA Astrophysics Data System (ADS)

    Sossah, A. M.; Zhou, H.-L.; Manson, S. T.; Hibbert, A.

    2009-05-01

    Photoionization cross sections are calculated for the ground ([Mg] 3p^63d4s^2 ^2D^e) state of atomic Sc for photon energies from threshold to 40.0 eV. The discrete Sc^+ orbitals are generated using both the AUTOSTRUCTURE and CIV3 codes, and R-matrix is used to carry out the cross section calculations. The results are compared with each other, then with previous calculations and available experimental data for final-ionic states representing the 3d and 4s main lines and associated satellites (ionization with excitation) in the region of the 3p -> 3d giant resonances [1]. Reasonably good agreement between our non-relativistic results and experiment is obtained. This work is supported by US DOE and NSF [4pt] [1] S. B. Whitfield, K. Kehoe, R. Wehlitz, M. O. Krause, and C. D. Caldwell ->hys. Rev. A 64, 022701 (2001).

  14. Coherent control of photoionization of atomic barium

    NASA Astrophysics Data System (ADS)

    Yamazaki, Rekishu

    We present the results of our study on coherent control of photoionization of atomic barium. Our study focused on the understanding of the controllability, especially due to the effect of the coherent interaction between the atomic system and the laser field. The first half of the study investigates the mechanisms of the control behind the previously observed laser phase-insensitive product state control. The controllability of this excitation scheme, two-color two-photon resonantly enhanced excitation, was analyzed from two aspects, the role of ac Stark shift introduced by the strong laser field and the multi-pathway quantum mechanical interferences. We have analyzed the excitation scheme from the analysis of the photoelectron angular distribution measured using the excitation scheme and the monitoring of the intermediate state population. Analysis of the data as well as the numerical simulation showed clear understanding of the role of two mechanisms in the product state control reported. We also investigated the control of the phase lag during the product state control. We conducted the control of the phase lag in the study of asymmetric photoelectron angular distribution, which arises from the concurrent even-odd parity outgoing electron wave excitation. The phase lag was controlled in full range, 2pi, and the results were analyzed in terms of the role of autoionizing resonance structures as well as the nature of outgoing electron waves at different locations of the autoionizing resonances.

  15. 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}.

  16. 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.

  17. Effects of anisotropic electron-ion interactions in atomic photoelectron angular distributions

    NASA Technical Reports Server (NTRS)

    Dill, D.; Starace, A. F.; Manson, S. T.

    1975-01-01

    A summary of the angular momentum transfer formulation of the differential photoionization cross section is presented and photoionization amplitudes in LS coupling are considered. The application of the theoretical concepts and relations developed is illustrated with the aid of an example involving the calculation of the angular distribution of photoelectrons ionized from atomic sulfur according to a certain reaction. The investigation shows that anisotropic electron-ion interactions in atomic sulfur lead to measurable differences between photoelectron angular distribution asymmetry parameters corresponding to alternative ionic term levels.

  18. Size Effects in Angle-Resolved Photoelectron Spectroscopy of Free Rare-Gas Clusters

    SciTech Connect

    Rolles, D.; Zhang, H.; Pesic, Z.D.; Bilodeau, R.C.; Wills, A.; Kukk, E.; Rude, B.S.; Ackerman, G.D.; Bozek, J.D.; Muino, R.D.; de Abajo, F.J.G.; Berrah, N.; /Western Michigan U. /LBNL, ALS /Turku U. /SLAC /Basque U., San Sebastian /Madrid, Inst. Optica

    2007-05-23

    The photoionization of free Xe clusters is investigated by angle-resolved time-of-flight photoelectron spectroscopy. The measurements probe the evolution of the photoelectron angular distribution parameter as a function of photon energy and cluster size. While the overall photon-energy-dependent behavior of the photoelectrons from the clusters is very similar to that of the free atoms, distinct differences in the angular distribution point at cluster-size-dependent effects. Multiple scattering calculations trace their origin to elastic photoelectron scattering.

  19. The combined use of a singly charged ion beam and undulator radiation for photoelectron spectrometry studies on atomic ions

    NASA Astrophysics Data System (ADS)

    Bizau, J. M.; Cubaynes, D.; Richter, M.; Wuilleumier, F.; Obert, J.; Putaux, J. C.

    1992-01-01

    We present the first photoelectron spectrometry experiment on a singly charged ion beam. Taking advantage of the high photon flux emitted in the undulator SU6 of Super-ACO, we have measured photoelectron spectra produced in the resonant photoionization of Ca+ ions at 33.2-eV photon energy. The success of this experiment depended strongly on the photon flux available. We demonstrate the capability of photoelectron spectrometry to precisely calibrate the photon spectrum emitted in the undulator.

  20. FAST TRACK COMMUNICATION: Generalized geometrical model for photoionization of polarized atoms: II. Magnetic dichroism in the 3p photoemission from the K 3p64s 2S1/2 ground state

    NASA Astrophysics Data System (ADS)

    Grum-Grzhimailo, A. N.; Cubaynes, D.; Heinecke, E.; Hoffmann, P.; Zimmermann, P.; Meyer, M.

    2010-10-01

    The generalized geometrical model for photoionization from polarized atoms is extended to include mixing of configurations in the initial atomic and/or the final photoion states. The theoretical results for angle-resolved linear and circular magnetic dichroism are in good agreement with new high-resolution photoelectron data for 3p-1 photoionization of potassium atoms polarized in the K 3p64s 2S1/2 ground state by laser optical pumping.

  1. Confinement resonances in photoionization of Xe@C₆₀+.

    PubMed

    Kilcoyne, A L D; Aguilar, A; Müller, 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 C60 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@C₆₀+ ion beam. The phenomenon was observed in the Xe@C(58)(3+) product ion channel. [corrected] PMID:21231297

  2. 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.

  3. 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.

  4. Coincidence Proportional Counter

    DOEpatents

    Manley, J H

    1950-11-21

    A coincidence proportional counter having a plurality of collecting electrodes so disposed as to measure the range or energy spectrum of an ionizing particle-emitting source such as an alpha source, is disclosed.

  5. Photoionization of cold gas phase coronene and its clusters: Autoionization resonances in monomer, dimer, and trimer and electronic structure of monomer cation

    NASA Astrophysics Data System (ADS)

    Bréchignac, Philippe; Garcia, Gustavo A.; Falvo, Cyril; Joblin, Christine; Kokkin, Damian; Bonnamy, Anthony; Parneix, Pascal; Pino, Thomas; Pirali, Olivier; Mulas, Giacomo; Nahon, Laurent

    2014-10-01

    Polycyclic aromatic hydrocarbons (PAHs) are key species encountered in a large variety of environments such as the Interstellar Medium (ISM) and in combustion media. Their UV spectroscopy and photodynamics in neutral and cationic forms are important to investigate in order to learn about their structure, formation mechanisms, and reactivity. Here, we report an experimental photoelectron-photoion coincidence study of a prototypical PAH molecule, coronene, and its small clusters, in a molecular beam using the vacuum ultraviolet (VUV) photons provided by the SOLEIL synchrotron facility. Mass-selected high resolution threshold photoelectron (TPES) and total ion yield spectra were obtained and analyzed in detail. Intense series of autoionizing resonances have been characterized as originating from the monomer, dimer, and trimer neutral species, which may be used as spectral fingerprints for their detection in the ISM by VUV absorption spectroscopy. Finally, a full description of the electronic structure of the monomer cation was made and discussed in detail in relation to previous spectroscopic optical absorption data. Tentative vibrational assignments in the near-threshold TPES spectrum of the monomer have been made with the support of a theoretical approach based on density functional theory.

  6. Photoionization of cold gas phase coronene and its clusters: Autoionization resonances in monomer, dimer, and trimer and electronic structure of monomer cation

    SciTech Connect

    Bréchignac, Philippe Falvo, Cyril; Parneix, Pascal; Pino, Thomas; Pirali, Olivier; Garcia, Gustavo A.; Nahon, Laurent; Joblin, Christine; Kokkin, Damian; Bonnamy, Anthony; Mulas, Giacomo

    2014-10-28

    Polycyclic aromatic hydrocarbons (PAHs) are key species encountered in a large variety of environments such as the Interstellar Medium (ISM) and in combustion media. Their UV spectroscopy and photodynamics in neutral and cationic forms are important to investigate in order to learn about their structure, formation mechanisms, and reactivity. Here, we report an experimental photoelectron-photoion coincidence study of a prototypical PAH molecule, coronene, and its small clusters, in a molecular beam using the vacuum ultraviolet (VUV) photons provided by the SOLEIL synchrotron facility. Mass-selected high resolution threshold photoelectron (TPES) and total ion yield spectra were obtained and analyzed in detail. Intense series of autoionizing resonances have been characterized as originating from the monomer, dimer, and trimer neutral species, which may be used as spectral fingerprints for their detection in the ISM by VUV absorption spectroscopy. Finally, a full description of the electronic structure of the monomer cation was made and discussed in detail in relation to previous spectroscopic optical absorption data. Tentative vibrational assignments in the near-threshold TPES spectrum of the monomer have been made with the support of a theoretical approach based on density functional theory.

  7. Photoionization of cold gas phase coronene and its clusters: autoionization resonances in monomer, dimer, and trimer and electronic structure of monomer cation.

    PubMed

    Bréchignac, Philippe; Garcia, Gustavo A; Falvo, Cyril; Joblin, Christine; Kokkin, Damian; Bonnamy, Anthony; Parneix, Pascal; Pino, Thomas; Pirali, Olivier; Mulas, Giacomo; Nahon, Laurent

    2014-10-28

    Polycyclic aromatic hydrocarbons (PAHs) are key species encountered in a large variety of environments such as the Interstellar Medium (ISM) and in combustion media. Their UV spectroscopy and photodynamics in neutral and cationic forms are important to investigate in order to learn about their structure, formation mechanisms, and reactivity. Here, we report an experimental photoelectron-photoion coincidence study of a prototypical PAH molecule, coronene, and its small clusters, in a molecular beam using the vacuum ultraviolet (VUV) photons provided by the SOLEIL synchrotron facility. Mass-selected high resolution threshold photoelectron (TPES) and total ion yield spectra were obtained and analyzed in detail. Intense series of autoionizing resonances have been characterized as originating from the monomer, dimer, and trimer neutral species, which may be used as spectral fingerprints for their detection in the ISM by VUV absorption spectroscopy. Finally, a full description of the electronic structure of the monomer cation was made and discussed in detail in relation to previous spectroscopic optical absorption data. Tentative vibrational assignments in the near-threshold TPES spectrum of the monomer have been made with the support of a theoretical approach based on density functional theory. PMID:25362317

  8. Decoherence in Attosecond Photoionization

    SciTech Connect

    Pabst, Stefan; Santra, Robin; Greenman, Loren; Mazziotti, David A.; Ho, Phay J.

    2011-02-04

    The creation of superpositions of hole states via single-photon ionization using attosecond extreme-ultraviolet pulses is studied with the time-dependent configuration-interaction singles (TDCIS) method. Specifically, the degree of coherence between hole states in atomic xenon is investigated. We find that interchannel coupling not only affects the hole populations, but it also enhances the entanglement between the photoelectron and the remaining ion, thereby reducing the coherence within the ion. As a consequence, even if the spectral bandwidth of the ionizing pulse exceeds the energy splittings among the hole states involved, perfectly coherent hole wave packets cannot be formed. For sufficiently large spectral bandwidth, the coherence can only be increased by increasing the mean photon energy.

  9. Decoherence in attosecond photoionization.

    PubMed

    Pabst, Stefan; Greenman, Loren; Ho, Phay J; Mazziotti, David A; Santra, Robin

    2011-02-01

    The creation of superpositions of hole states via single-photon ionization using attosecond extreme-ultraviolet pulses is studied with the time-dependent configuration-interaction singles (TDCIS) method. Specifically, the degree of coherence between hole states in atomic xenon is investigated. We find that interchannel coupling not only affects the hole populations, but it also enhances the entanglement between the photoelectron and the remaining ion, thereby reducing the coherence within the ion. As a consequence, even if the spectral bandwidth of the ionizing pulse exceeds the energy splittings among the hole states involved, perfectly coherent hole wave packets cannot be formed. For sufficiently large spectral bandwidth, the coherence can only be increased by increasing the mean photon energy. PMID:21405393

  10. Time-resolved photoelectron spectroscopy of liquids

    NASA Astrophysics Data System (ADS)

    Buchner, Franziska; Lübcke, Andrea; Heine, Nadja; Schultz, Thomas

    2010-11-01

    We present a novel setup for the investigation of ultrafast dynamic processes in a liquid jet using time-resolved photoelectron spectroscopy. A magnetic-bottle type spectrometer with a high collection efficiency allows the very sensitive detection of photoelectrons emitted from a 10 μm thick liquid jet. This translates into good signal/noise ratio and rapid data acquisition making femtosecond time-resolved experiments feasible. We describe the experimental setup, a detailed spectrometer characterization based on the spectroscopy of nitric oxide in the gas phase, and results from femtosecond time-resolved experiments on sodium iodide solutions. The latter experiments reveal the formation and evolution of the solvated electron and we characterize two distinct spectral components corresponding to initially thermalized and unthermalized solvated electrons. The absence of dark states in photoionization, the direct measurement of electron binding energies, and the ability to resolve dynamic processes on the femtosecond time scale make time-resolved photoelectron spectroscopy from the liquid jet a very promising method for the characterization of photochemical processes in liquids.

  11. Time-resolved photoelectron spectroscopy of liquids.

    PubMed

    Buchner, Franziska; Lübcke, Andrea; Heine, Nadja; Schultz, Thomas

    2010-11-01

    We present a novel setup for the investigation of ultrafast dynamic processes in a liquid jet using time-resolved photoelectron spectroscopy. A magnetic-bottle type spectrometer with a high collection efficiency allows the very sensitive detection of photoelectrons emitted from a 10 μm thick liquid jet. This translates into good signal/noise ratio and rapid data acquisition making femtosecond time-resolved experiments feasible. We describe the experimental setup, a detailed spectrometer characterization based on the spectroscopy of nitric oxide in the gas phase, and results from femtosecond time-resolved experiments on sodium iodide solutions. The latter experiments reveal the formation and evolution of the solvated electron and we characterize two distinct spectral components corresponding to initially thermalized and unthermalized solvated electrons. The absence of dark states in photoionization, the direct measurement of electron binding energies, and the ability to resolve dynamic processes on the femtosecond time scale make time-resolved photoelectron spectroscopy from the liquid jet a very promising method for the characterization of photochemical processes in liquids. PMID:21133461

  12. Sum rules for the polarization correlations in photoionization and bremsstrahlung

    NASA Astrophysics Data System (ADS)

    Pratt, R. H.; Müller, R. A.; Surzhykov, A.

    2016-05-01

    The polarization correlations in doubly differential cross sections are investigated for photoionization and ordinary bremsstrahlung. These correlations describe the polarization transfer between incident light and ejected photoelectrons as well as between an incoming electron beam and bremsstrahlung light, respectively. They are characterized by a set of seven real parameters Ci j. We show that the squares of these parameters are connected by simple "sum rules." These sum rules can be applied for both one-electron systems and also for atoms, if the latter are described within the independent particle approximation. In particular, they are exact in their simplest form (i) for the photoionization of K -, LI ,I I-, and MI ,I I-atomic shells, as well as (ii) for bremsstrahlung in which the electron is scattered into s1 /2 or p1 /2 states, as in the tip (bremsstrahlung) region. Detailed calculations are performed to verify the derived identities and to discuss their possible applications for the analysis of modern photoionization and bremsstrahlung experiments. In particular, we argue that the sum rules may help to determine the entire set of (significant) polarization correlations in the case when not all Ci j are available for experimental observation.

  13. Time delay in molecular photoionization

    NASA Astrophysics Data System (ADS)

    Hockett, P.; Frumker, E.; Villeneuve, D. M.; Corkum, P. B.

    2016-05-01

    Time-delays in the photoionization of molecules are investigated. As compared to atomic ionization, the time-delays expected from molecular ionization present a much richer phenomenon, with a strong spatial dependence due to the anisotropic nature of the molecular scattering potential. We investigate this from a scattering theory perspective, and make use of molecular photoionization calculations to examine this effect in representative homonuclear and hetronuclear diatomic molecules, nitrogen and carbon monoxide. We present energy and angle-resolved maps of the Wigner delay time for single-photon valence ionization, and discuss the possibilities for experimental measurements.

  14. Quantum beat oscillations in the two-color-photoionization continuum of neon and their dependence on the intensity of the ionizing laser pulse

    SciTech Connect

    Geiseler, Henning; Rottke, Horst; Steinmeyer, Guenter; Sandner, Wolfgang

    2011-09-15

    We investigate quantum beat oscillations in the photoionization continuum of Ne atoms that are photoionized by absorption of two photons via a group of excited bound states using ultrashort extreme ultraviolet and infrared laser pulses. The extreme ultraviolet pulse starts an excited-state wave packet that is photoionized by a high-intensity infrared pulse after a variable time delay. We analyze the continuum quantum beats from this two-step photoionization process and their dependence on the photoelectron kinetic energy. We find a pronounced dependence of the quantum beat amplitudes on the photoelectron kinetic energy. The dependence changes significantly with the applied infrared laser-pulse intensity. The experimental results are in good qualitative agreement with a model calculation that is adapted to the experimental situation. It accounts for the intensity dependence of the quantum beat structure through the coupling of the excited-state wave packet to other bound Ne states induced by the high-intensity infrared laser pulse.

  15. Packet narrowing and quantum entanglement in photoionization and photodissociation

    SciTech Connect

    Fedorov, M.V.; Efremov, M.A.; Kazakov, A.E.; Chan, K.W.; Eberly, J.H.; Law, C.K.

    2004-05-01

    The narrowing of electron and ion wave packets in the process of photoionization is investigated, with the electron-ion recoil taken fully into account. Packet localization of this type is directly related to entanglement in the joint quantum state of the electron and ion, and to Einstein-Podolsky-Rosen localization. Experimental observation of such packet-narrowing effects is suggested via coincidence registration by two detectors, with a fixed position of one and varying position of the other. A similar effect, typically with an enhanced degree of entanglement, is shown to occur in the case of photodissociation of molecules.

  16. Relativistic effects in the photoionization of hydrogen-like ions with screened Coulomb interaction

    SciTech Connect

    Xie, L. Y.; Wang, J. G.; Janev, R. K.

    2014-06-15

    The relativistic effects in the photoionization of hydrogen-like ion with screened Coulomb interaction of Yukawa type are studied for a broad range of screening lengths and photoelectron energies. The bound and continuum wave functions have been determined by solving the Dirac equation. The study is focused on the relativistic effects manifested in the characteristic features of photoionization cross section for electric dipole nl→ε,l±1 transitions: shape resonances, Cooper minima and cross section enhancements due to near-zero-energy states. It is shown that the main source of relativistic effects in these cross section features is the fine-structure splitting of bound state energy levels. The relativistic effects are studied in the photoionization of Fe{sup 25+} ion, as an example.

  17. 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)

  18. Photoionization in the Solar Wind

    NASA Astrophysics Data System (ADS)

    Landi, E.; Lepri, S. T.

    2015-10-01

    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 O7+/O6+ 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 O7+/O6+ ratio needs to be used with caution for solar wind classification and coronal temperature estimates, and recommend the C6+/C4+ ratio for these purposes.

  19. Valence and inner-valence shell dissociative photoionization of CO in the 26-33 eV range. I. Ion-electron kinetic energy correlation and laboratory frame photoemission.

    PubMed

    Lebech, M; Houver, J C; Dowek, D

    2009-05-21

    The (V(A+), V(e), ê) vector correlation method, combining imaging and time-of-flight resolved electron-ion coincidence techniques, is used to probe dissociative photoionization (DPI) of CO induced by vacuum ultra violet linearly or circularly polarized synchrotron radiation in the 26-33 eV photon excitation energy range. It provides original information about both the photoionization dynamics of the CO molecule and the dissociation dynamics of the CO(+) molecular ions. The explored region corresponds to valence and inner-valence CO(+) ionic states, which involve doubly or multiply excited electronic configurations. In this paper I we identify up to 17 DPI reaction pathways by the position of the intermediate CO(+) molecular states in the Franck-Condon region and the (C(+) + O) or (O(+) + C) dissociation limits to which they correlate. For these processes we report the laboratory frame beta(C+/O+) and beta(e) asymmetry parameters as well as the relative branching ratios in selected binding energy bands. The I(chi,theta(e),phi(e)) molecular frame photoelectron angular distributions for selected PI processes will be reported in a companion paper II and compared with multichannel Schwinger configuration interaction ab initio calculations of these observables. PMID:19466836

  20. Hartree-Fock calculation of the differential photoionization cross sections of small Li clusters

    NASA Astrophysics Data System (ADS)

    Galitskiy, S. A.; Artemyev, A. N.; Jänkälä, K.; Lagutin, B. M.; Demekhin, Ph. V.

    2015-01-01

    Cross sections and angular distribution parameters for the single-photon ionization of all electron orbitals of Li2-8 are systematically computed in a broad interval of the photoelectron kinetic energies for the energetically most stable geometry of each cluster. Calculations of the partial photoelectron continuum waves in clusters are carried out by the single center method within the Hartree-Fock approximation. We study photoionization cross sections per one electron and analyze in some details general trends in the photoionization of inner and outer shells with respect to the size and geometry of a cluster. The present differential cross sections computed for Li2 are in a good agreement with the available theoretical data, whereas those computed for Li3-8 clusters can be considered as theoretical predictions.

  1. Hartree-Fock calculation of the differential photoionization cross sections of small Li clusters.

    PubMed

    Galitskiy, S A; Artemyev, A N; Jänkälä, K; Lagutin, B M; Demekhin, Ph V

    2015-01-21

    Cross sections and angular distribution parameters for the single-photon ionization of all electron orbitals of Li2-8 are systematically computed in a broad interval of the photoelectron kinetic energies for the energetically most stable geometry of each cluster. Calculations of the partial photoelectron continuum waves in clusters are carried out by the single center method within the Hartree-Fock approximation. We study photoionization cross sections per one electron and analyze in some details general trends in the photoionization of inner and outer shells with respect to the size and geometry of a cluster. The present differential cross sections computed for Li2 are in a good agreement with the available theoretical data, whereas those computed for Li3-8 clusters can be considered as theoretical predictions. PMID:25612708

  2. Highly Efficient State-Selective Submicrosecond Photoionization Detection of Single Atoms

    SciTech Connect

    Henkel, F.; Krug, M.; Hofmann, J.; Rosenfeld, W.; Weber, M.; Weinfurter, H.

    2010-12-17

    We experimentally demonstrate a detection scheme suitable for state analysis of single optically trapped atoms in less than 1 {mu}s with an overall detection efficiency {eta} exceeding 98%. The method is based on hyperfine-state-selective photoionization and subsequent registration of the correlated photoion-electron pairs by coincidence counting via two opposing channel electron multipliers. The scheme enables the calibration of absolute detection efficiencies and might be a key ingredient for future quantum information applications or precision spectroscopy of ultracold atoms.

  3. FAST TRACK COMMUNICATION: Confinement resonances in the photoionization of endohedral atoms: myth or reality?

    NASA Astrophysics Data System (ADS)

    Korol, A. V.; Solov'yov, A. V.

    2010-10-01

    We demonstrate that the structure of confinement resonances in the photoionization cross section of an endohedral atom is very sensitive to the mean displacement langarang of the atom from the cage centre. The resonances are strongly suppressed if 2langarang exceeds the photoelectron half-wavelength. We explain the results of recent experiments which contradict the earlier theoretical predictions on the existence of confinement resonances in particular endohedral systems.

  4. Photoionization cross sections for atomic chlorine using an open-shell random phase approximation

    NASA Technical Reports Server (NTRS)

    Starace, A. F.; Armstrong, L., Jr.

    1975-01-01

    The use of the Random Phase Approximation with Exchange (RPAE) for calculating partial and total photoionization cross sections and photoelectron angular distributions for open shell atoms is examined for atomic chlorine. Whereas the RPAE corrections in argon (Z=18) are large, it is found that those in chlorine (Z=17) are much smaller due to geometric factors. Hartree-Fock calculations with and without core relaxation are also presented. Sizable deviations from the close coupling results of Conneely are also found.

  5. Photoionization indicators of optical mixing of different-parity degenerate Rydberg states

    NASA Astrophysics Data System (ADS)

    Parzyński, R.; Sobczak, M.; Wójcik, A.

    2000-02-01

    We discuss a photoionization version of the photoexcitation model of Corless and Stroud [Phys. Rev. Lett. 79, 637 (1997)]. In the photoexcitation model, a np hydrogenic state of n>>1 was excited from the ground 1s state and the excited population was allowed to migrate to other angular momentum states within the one n only due to strongly nonresonant electric-dipole \\|Δn\\|=0, \\|Δl\\|=1 Rydberg-to-Rydberg couplings. When, as is the essence of the photoexcitation model, the same one n-manifold approximation is made in the model of high-n Rydberg-state photoionization, a number of interesting photoionization effects are obtained. Among them, the most spectacular seems to be the emission of photoelectrons in the ``forbidden'' directions and the suppression of ionization when compared to the Fermi golden rule predictions. However, we show on the basis of an approximate analysis that these photoionization effects can be strongly diminished when additional n manifolds around the selected one are included in the model. Thus, we conclude that the one n-manifold approximation overestimates results when applied to the problem of high-n Rydberg-state photoionization.

  6. Coincident disruptive coloration

    PubMed Central

    Cuthill, Innes C.; Székely, Aron

    2008-01-01

    Even if an animal matches its surroundings perfectly in colour and texture, any mismatch between the spatial phase of its pattern and that of the background, or shadow created by its three-dimensional relief, is potentially revealing. Nevertheless, for camouflage to be fully broken, the shape must be recognizable. Disruptive coloration acts against object recognition by the use of high-contrast internal colour boundaries to break up shape and form. As well as the general outline, characteristic features such as eyes and limbs must also be concealed; this can be achieved by having the colour patterns on different, but adjacent, body parts aligned to match each other (i.e. in phase). Such ‘coincident disruptive coloration’ ensures that there is no phase disjunction where body parts meet, and causes different sections of the body to blend perceptually. We tested this theory using field experiments with predation by wild birds on artificial moth-like targets, whose wings and (edible pastry) bodies had colour patterns that were variously coincident or not. We also carried out an experiment with humans searching for analogous targets on a computer screen. Both experiments show that coincident disruptive coloration is an effective mechanism for concealing an otherwise revealing body form. PMID:18990668

  7. Use of threshold electron and fluorescence coincidence techniques to probe the decay dynamics of the valence states of CF + 4, SiF + 4, SiCl + 4, and GeCl + 4

    NASA Astrophysics Data System (ADS)

    Smith, D. M.; Tuckett, R. P.; Yoxall, K. R.; Codling, K.; Hatherly, P. A.; Aarts, J. F. M.; Stankiewicz, M.

    1994-12-01

    Threshold photoelectron-photoion coincidence (TPEPICO), photoion-fluorescence coincidence (PIFCO), and threshold photoelectron-fluorescence coincidence (TPEFCO) spectroscopies have been used to measure, state selectively, the decay pathways of all the valence states of four gas-phase tetrahedral ion CF+4, SiF+4, SiCl+4, and GeCl+4 in the range 11-26 eV. Vacuum UV radiation from a synchrotron source dispersed by a 5 m normal-incidence McPherson monochromator ionizes the parent molecule, and electrons and ions are detected by threshold electron analysis and time-of-flight mass spectrometry, respectively. Undispersed fluorescence from the interaction region can also be detected, allowing the three different types of coincidence experiment to be performed. The optimum resolution of the monochromator is matched to that of the threshold analyzer, and this work improves on preliminary results using a 1 m Seya monochromator [Chem. Phys. 174, 441 and 453 (1993)] where the resolution of the spectra was limited by that of the optical source. TPEPICO spectra are recorded continuously as a function of photon energy, allowing both threshold photoelectron spectra and yields of all the fragment ions to be obtained. Kinetic energy releases can also be measured at fixed photon energies with good time resolution. PIFCO and TPEFCO spectra are recorded at fixed photon energies. The former experiment can yield the fate of the lower electronic state of the parent ion to which fluorescence occurs. The latter experiment yields the lifetime of the fluorescing state; with sufficient resolution of the photoionizing radiation, the lifetime is specific to one vibrational level of the emitting electronic state. For CF+4 and SiF+4 work has concentrated on the third and fourth excited states, C˜ 2T2 and D˜ 2A1, of which only the C˜ state of SiF+4 does not decay radiatively. Vibrationally state-selected fluorescence quantum yields and lifetimes have been measured for four levels of the C˜ state

  8. Graphene Membranes for Atmospheric Pressure Photoelectron Spectroscopy.

    PubMed

    Weatherup, Robert S; Eren, Baran; Hao, Yibo; Bluhm, Hendrik; Salmeron, Miquel B

    2016-05-01

    Atmospheric pressure X-ray photoelectron spectroscopy (XPS) is demonstrated using single-layer graphene membranes as photoelectron-transparent barriers that sustain pressure differences in excess of 6 orders of magnitude. The graphene serves as a support for catalyst nanoparticles under atmospheric pressure reaction conditions (up to 1.5 bar), where XPS allows the oxidation state of Cu nanoparticles and gas phase species to be simultaneously probed. We thereby observe that the Cu(2+) oxidation state is stable in O2 (1 bar) but is spontaneously reduced under vacuum. We further demonstrate the detection of various gas-phase species (Ar, CO, CO2, N2, O2) in the pressure range 10-1500 mbar including species with low photoionization cross sections (He, H2). Pressure-dependent changes in the apparent binding energies of gas-phase species are observed, attributable to changes in work function of the metal-coated grids supporting the graphene. We expect atmospheric pressure XPS based on this graphene membrane approach to be a valuable tool for studying nanoparticle catalysis. PMID:27082434

  9. Photoionization study of quasibound states of doubly charged molecular nitrogen ions

    NASA Astrophysics Data System (ADS)

    Hellner, L.; Besnard, M. J.; Dujardin, G.; Malinovich, Y.

    1988-01-01

    Doubly charged N 22+ ions were produced by double photoionization of neutral nitrogen molecules with the synchrotron radiation from ACO as a photon source of variable energy in the 40-70 eV range. From the double photoionization spectrum the threshold energy of the stable X 1Σ g+ state was found at 43.1 ± 0.1 eV. The D 1Σ g+ → X 1Σ g+ emission observed by using a photoion-photon of fluorescence coincidence (PIFCO) experiment. The onset energy of this emitting D 1Σ u+ state at 50.5 eV, was deduced from the variation of the fluorescence efficiency as a function of the excitation photon energy. The lifetime of this emitting state was measured to be τ = 8 ± 3 ns.

  10. 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.

  11. Quantum interference in laser-assisted photoionization and analytical methods for the measurement of an attosecond xuv pulse

    SciTech Connect

    Ge Yucheng; He Haiping

    2011-08-15

    Investigations of the quantum interference in laser-assisted photoionization by an attosecond extreme ultraviolet (xuv) pulse shows an approximately constant value for the total photoionizations for different laser intensities. The square of the full width at half maximum of a photoelectron energy spectrum (PES) linearly depends on the laser intensity. By determining the laser-related phase of each streaked electron and using a transfer equation with linear corrections, an analytically quick method is proposed for precisely reconstructing the xuv pulse intensity (chirp) from one (two) measured PES(s) with a theoretical root-mean-square temporal (energy) difference of less than 1 attosecond (0.1 eV).

  12. High-resolution pulsed-field ionization photoelectron spectroscopy using multi-bunch synchrotron radiation

    SciTech Connect

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

    1997-04-01

    BL9.0.2.2 is the newly constructed experimental End Station 2 at the Chemical Dynamics Beamline 9.0.2 of the Advanced Light Source (ALS). It is dedicated to the high resolution photoionization study of molecules of interest to atmospheric and combustion chemistry. This End Station is equipped with a high resolution scanning monochromator, which has been demonstrated to have a world record resolution of E/{delta}E=70,000. Taking the advantage of the high resolution ALS light, the authors have improved the energy resolution in threshold photoelectron spectroscopy (TPES) to 0.8 meV. The TPES is a popular technique for photoionization experiments at all synchrotron radiation facilities due to its high energy resolution as compared to that of traditional photoelectron spectroscopy (PES). TPES achieves higher energy resolution by preferentially detecting near zero kinetic energy photoelectrons resulting from threshold photoionization. However, the spectra obtained from the TPES technique generally are complicated by the simultaneous detection of electrons with nonzero kinetic energy, which are not fully discriminated against. On the other hand, the spectra obtained from pulsed field ionization photoelectron spectroscopy (PFI-PES) are completely free of the contamination from kinetic electrons. The PFI-PE technique basically involves the detection of the photoelectrons from field ionization of the very high-n Rydberg states, a few cm{sup {minus}1} below the ionization energy (IE), by applying a delayed pulsed electric field. Within a delay of a few microseconds, all the prompt electrons formed from direct ionization will escape from the photoionization region and will not be collected. The authors have recently overcome problems with energy resolution of an electron time-of-flight technique, and incorporated the PFI-PE technique with multi-bunch VUV synchrotron radiation.

  13. Tunable wavelength soft photoionization of ionic liquid vapors

    SciTech Connect

    Strasser, Daniel; Goulay, Fabien; Belau, Leonid; Kostko, Oleg; Koh, Christine; Chambreau, Steven D.; Vaghjiani, Ghanshyam L.; Ahmed, Musahid; Leone, Stephen R.

    2009-11-11

    Combined data of photoelectron spectra and photoionization efficiency curves in the near threshold ionization region of isolated ion-pairs from [emim][Tf2N], [emim][Pf2N]and [dmpim][Tf2N]ionic liquid vapors reveal small shifts in the ionization energies of ion-pair systems due to cation and anion substitutions. Shifts towards higher binding energy following anion substitution are attributed to increased electronegativity of the anion itself, while shifts towards lower binding energies following cation substitution are attributed to an increase in the cation-anion distance that causes a lower Coulombic binding potential. The predominant ionization mechanism in the near threshold photon energy region is identified as dissociative ionization, involving dissociation of the ion-pair and the production of intact cations as the positively charged products.

  14. 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.

  15. 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.

  16. Photoionization of the outer electrons in noble gas endohedral atoms

    SciTech Connect

    Amusia, M. Ya. Baltenkov, A. S.; Chernysheva, L. V.

    2008-08-15

    We suggest a prominent modification of the outer shell photoionization cross section in noble gas (NG) endohedral atoms NG-C{sub n} under the action of the electron shell of fullerene C{sub n}. This shell leads to two important effects: a strong enhancement of the cross section due to fullerene shell polarization under the action of the incoming electromagnetic wave and to prominent oscillation of this cross section due to the reflection of a photoelectron from the NG by the fullerene shell. Both factors lead to powerful maxima in the outer shell ionization cross sections of NG-C{sub n}, which we call giant endohedral resonances. The oscillator strength reaches a very large value in the atomic scale, 25. We consider atoms of all noble gases except He. The polarization of the fullerene shell is expressed in terms of the total photoabsorption cross section of the fullerene. The photoelectron reflection is taken into account in the framework of the so-called bubble potential, which is a spherical {delta}-type potential. It is assumed in the derivations that the NG is centrally located in the fullerene. It is also assumed, in accordance with the existing experimental data, that the fullerene radius R{sub C} is much larger than the atomic radius r{sub A} and the thickness {delta}{sub C} of the fullerene shell. As was demonstrated recently, these assumptions allow us to represent the NG-C{sub n} photoionization cross section as a product of the NG cross section and two well-defined calculated factors.

  17. Photoabsorption and photoionization of HD

    SciTech Connect

    Dehmer, Patricia M.; Chupka, William A.

    1983-01-01

    Relative photoabsorption and photoionization cross sections have been measured for HD at a temperature of 78 K in the wavelength region from 735 to 805 Â. The present wavelength resolution of 0.016 Â represents an improvement of more than two orders of magnitude over that of previous photoionization studies of this molecule. Bands of the 3pπ D ¹Πu←X ¹Σg⁺ system are observed to v'=17, and ionization efficiencies are reported for a number of Rydberg states of low principal quantum number. As in the case of H2, the ionization efficiency is close to unity for Rydberg states that can autoionize with Δv= -1, but drops to zero for states that can autoionize only with a large change in vibrational quantum number and that are significantly predissociated (such as the 3pπ D ¹Πu state). The breakdown of (g,u) symmetry in HD and the resulting effects on the absorption spectrum and on the decay paths of the Rydberg states are discussed.

  18. Measurements of meteor smoke particles during the ECOMA-2006 campaign: 1. Particle detection by active photoionization

    NASA Astrophysics Data System (ADS)

    Rapp, Markus; Strelnikova, Irina

    2009-03-01

    We present a new design of an in situ detector for the study of meteor smoke particles (MSPs) in the middle atmosphere. This detector combines a classical Faraday cup with a xenon-flashlamp for the active photoionization/photodetachment of MSPs and the subsequent detection of corresponding photoelectrons. This instrument was successfully launched in September 2006 from the Andøya Rocket Range in Northern Norway. A comparison of photocurrents measured during this rocket flight and measurements performed in the laboratory proves that observed signatures are truly due to photoelectrons. In addition, the observed altitude cut-off at 60 km (i.e., no signals were observed below this altitude) is fully understood in terms of the mean free path of the photoelectrons in the ambient atmosphere. This interpretation is also proven by a corresponding laboratory experiment. Consideration of all conceivable species which can be ionized by the photons of the xenon-flashlamp demonstrates that only MSPs can quantitatively explain the measured currents below an altitude of 90 km. Above this altitude, measured photocurrents are most likely due to photoionization of nitric oxide. In conclusion, our results demonstrate that the active photoionization and subsequent detection of photoelectrons provides a promising new tool for the study of MSPs in the middle atmosphere. Importantly, this new technique does not rely on the a priori charge of the particles, neither is the accessible particle size range severely limited by aerodynamical effects. Based on the analysis described in this study, the geophysical interpretation of our measurements is presented in the companion paper by Strelnikova, I., et al. [2008. Measurements of meteor smoke particles during the ECOMA-2006 campaign: 2. results. Journal of Atmospheric and Solar-Terrestrial Physics, this issue, doi:10.1016/j.jastp.2008.07.011].

  19. Spin-Orbit Activated Interchannel Coupling Effect in Dipole and Quadrupole Photoionization

    NASA Astrophysics Data System (ADS)

    Kumar, S. Sunil; Deschmukh, P. C.; Banerjee, T.; Manson, S. T.

    2008-05-01

    Spin-orbit activated interchannel coupling has been found to affect photoelectron parameters in both the dipole and quadrupole manifolds [1-3]. This effect has been reported in the dipole photoionization parameters of 3d subshells of Xe [1], Ba [1, 3] and Cs [1, 3] and quadrupole spin-polarization parameters of Xe 3d [2]. In the present work, dipole and quadrupole photoionization from 4d and 4p subshells of Xe and 5d and 5p subshells of Rn have been investigated. The effect is significant in dipole photoionization of Xe 4d and Rn 5d, and in quadrupole photoionization of Xe 4p and of Rn 5p states. [1] M. Ya. Amusia, L. V. Chernysheva, S. T. Manson, A. M. Msezane, and V. Radojevic, Phys. Rev. Lett. 88 093002 (2002). [2] M. Ya. Amusia, N. A. Cherepkov, L. V. Chernysheva, Z. Felfli and A. Z. Msezane, J. Phys. B 38 1133 (2005). [3] T. Richter, E. Heinecke, P. Zimmermann, K. Godehusen, M. Yalcinkaya, D. Cubaynes, and M. Meyer, Phys. Rev. Lett. 98 143002 (2007).

  20. Dynamics of ultrafast internal conversion processes studied by femtosecond time-delayed photoelectron spectroscopy

    SciTech Connect

    Cyr, D.R.; Hayden, C.C.

    1995-08-01

    The authors have studied the dynamics of ultrafast internal conversion processes using femtosecond time-resolved photoionization and photoelectron spectroscopy. In hexatriene, following femtosecond pulse excitation at 250 nm, they use time-delayed photoionization to observe the formation and decay of an intermediate species on the subpicosecond time scale. With time-resolved photoelectron spectroscopy, the rapid evolution of vibrational excitation in this intermediate is observed, as electronic energy is converted to vibrational energy in the molecule. The photodynamics of cis and trans isomers of hexatriene are compared and found to be surprisingly different on the 2-3 psec time scale. These results are important for understanding the fundamental photochemical processes in linear polyenes, which have served as models for the active chromophores of many biological photosystems.

  1. Long-Range Coulomb Effect in Intense Laser-Driven Photoelectron Dynamics

    NASA Astrophysics Data System (ADS)

    Quan, Wei; Hao, Xiaolei; Chen, Yongju; Yu, Shaogang; Xu, Songpo; Wang, Yanlan; Sun, Renping; Lai, Xuanyang; Wu, Chengyin; Gong, Qihuang; He, Xiantu; Liu, Xiaojun; Chen, Jing

    2016-06-01

    In strong field atomic physics community, long-range Coulomb interaction has for a long time been overlooked and its significant role in intense laser-driven photoelectron dynamics eluded experimental observations. Here we report an experimental investigation of the effect of long-range Coulomb potential on the dynamics of near-zero-momentum photoelectrons produced in photo-ionization process of noble gas atoms in intense midinfrared laser pulses. By exploring the dependence of photoelectron distributions near zero momentum on laser intensity and wavelength, we unambiguously demonstrate that the long-range tail of the Coulomb potential (i.e., up to several hundreds atomic units) plays an important role in determining the photoelectron dynamics after the pulse ends.

  2. Long-Range Coulomb Effect in Intense Laser-Driven Photoelectron Dynamics

    PubMed Central

    Quan, Wei; Hao, XiaoLei; Chen, YongJu; Yu, ShaoGang; Xu, SongPo; Wang, YanLan; Sun, RenPing; Lai, XuanYang; Wu, ChengYin; Gong, QiHuang; He, XianTu; Liu, XiaoJun; Chen, Jing

    2016-01-01

    In strong field atomic physics community, long-range Coulomb interaction has for a long time been overlooked and its significant role in intense laser-driven photoelectron dynamics eluded experimental observations. Here we report an experimental investigation of the effect of long-range Coulomb potential on the dynamics of near-zero-momentum photoelectrons produced in photo-ionization process of noble gas atoms in intense midinfrared laser pulses. By exploring the dependence of photoelectron distributions near zero momentum on laser intensity and wavelength, we unambiguously demonstrate that the long-range tail of the Coulomb potential (i.e., up to several hundreds atomic units) plays an important role in determining the photoelectron dynamics after the pulse ends. PMID:27256904

  3. Long-Range Coulomb Effect in Intense Laser-Driven Photoelectron Dynamics.

    PubMed

    Quan, Wei; Hao, XiaoLei; Chen, YongJu; Yu, ShaoGang; Xu, SongPo; Wang, YanLan; Sun, RenPing; Lai, XuanYang; Wu, ChengYin; Gong, QiHuang; He, XianTu; Liu, XiaoJun; Chen, Jing

    2016-01-01

    In strong field atomic physics community, long-range Coulomb interaction has for a long time been overlooked and its significant role in intense laser-driven photoelectron dynamics eluded experimental observations. Here we report an experimental investigation of the effect of long-range Coulomb potential on the dynamics of near-zero-momentum photoelectrons produced in photo-ionization process of noble gas atoms in intense midinfrared laser pulses. By exploring the dependence of photoelectron distributions near zero momentum on laser intensity and wavelength, we unambiguously demonstrate that the long-range tail of the Coulomb potential (i.e., up to several hundreds atomic units) plays an important role in determining the photoelectron dynamics after the pulse ends. PMID:27256904

  4. Probing and extracting the structure of vibrating SF6 molecules with inner-shell photoelectrons

    NASA Astrophysics Data System (ADS)

    Nguyen, Ngoc-Ty; Lucchese, R. R.; Lin, C. D.; Le, Anh-Thu

    2016-06-01

    We propose a scheme for probing the structure of vibrating molecules with photoelectrons generated from ultrashort soft-x-ray pulses. As an example we analyze below-100-eV photoelectrons liberated from the S (2 p ) orbital of vibrating SF6 molecules to image very small structural changes of molecular vibration. In particular, photoionization cross sections and photoelectron angular distributions (PAD) at nonequilibrium geometries can be retrieved accurately with photoelectrons near the shape resonance at 13 eV. This is achieved with a pump-probe scheme, in which the symmetric stretch mode is first Raman excited predominantly by a relatively short laser pulse and then later probed at different time delays by a few-femtosecond soft-x-ray pulse with photon energy near 200 eV.

  5. Ratios of photoelectron to EUV ionization rates for aeronomic studies

    SciTech Connect

    Richards, P.G.; Torr, D.G. )

    1988-05-01

    This study reveals that the ratios of the photoelectron to EUV ionization rates are not constant but depend on the degree of attenuation of the solar EUV flux and on the transport of photoelectrons. At high altitudes in the absence of photoelectron transport, the O{sup +} and N{sub 2}{sup +} ionization rate ratios are about 0.35, but they increase with increasing optical depth to such an extent that in the vicinity of the ionization peak, photoelectron impact ionization is as important as photoionization for O{sup +} and N{sub 2}{sup +}. The O{sub 2}{sup +} ratio is about half that of O{sup +} at high altitudes adn also increases with increasing optical depth but reaches a peak of about 0.4. The authors present simple formulae which mimic the attenuation behavior of the ionization ratios. Transport effects become important above about 250 km where the ratios vary by a factor of 2 depending on the presence or absence of photoelectrons from the conjugate ionosphere. In addition to the photoelectron to EUV ionization ratios, they present photodissociative branching ratios for O{sub 2} and N{sub 2}. These photodissociative ratios are also a function of the degree of attenuation of the EUV flux. In the region where attenuation is not important, the N{sup +} to N{sub 2}{sup +} ratio is 0.14, and the O{sup +} to O{sub 2}{sup +} ratio is 0.22. There is a factor of 2 uncertainty in our calculated ratios on account of uncertainties in the solar EUV flux spectrum and also uncertainties in the electron impact cross sections.

  6. Single and double photoionization of Li2

    NASA Astrophysics Data System (ADS)

    Pindzola, M. S.; Li, Ye; Colgan, J.

    2015-01-01

    Time-dependent close-coupling methods are used to study the single and double photoionization of Li2. Formulations for both one-active and two-active electron methods make use of Hartree with local exchange potentials for the core electrons. Both the single and double photoionization cross sections for Li2 are found to be larger for linear polarization than for circular polarization, in sharp contrast to that found before for H2. In particular the double photoionization cross sections for Li2 are found to be approximately five times larger than for H2 and thus more easily observed by future experiments.

  7. Cluster beam analysis via photoionization

    SciTech Connect

    Grover, J.R. ); Herron, W.J.; Coolbaugh, M.T.; Peifer, W.R.; Garvey, J.F. )

    1991-08-22

    A photoionization method for quantitatively analyzing the neutral products of free jet expansions is described. The basic principle is to measure the yield of an ion characterization of each component cluster at a photon energy just below that at which production of the same ion from larger clusters can be detected. Since there is then no problem with fragmentation, the beam density of each neutral cluster can be measured in the presence of larger clusters. Although these measurements must be done in the test ions' onset regions where their yields are often quite small, the technique is made highly practicable by the large intensities of widely tunable vacuum-ultraviolet synchrotron light now available at electron storage rings. As an example, the method is applied to the analysis of cluster beams collimated from the free jet expansion of a 200:1 ammonia-chlorobenzene mixture.

  8. Complete photoionization experiments via ultrafast coherent control with polarization multiplexing.

    PubMed

    Hockett, P; Wollenhaupt, M; Lux, C; Baumert, T

    2014-06-01

    Photoelectron angular distributions (PADs) obtained from ionization of potassium atoms using moderately intense femtosecond IR fields (∼10^{12}  W cm^{-2}) of various polarization states are shown to provide a route to "complete" photoionization experiments. Ionization occurs by a net three-photon absorption process, driven via the 4s→4p resonance at the one-photon level. A theoretical treatment incorporating the intrapulse electronic dynamics allows for a full set of ionization matrix elements to be extracted from 2D imaging data. 3D PADs generated from the extracted matrix elements are also compared to experimental, tomographically reconstructed, 3D photoelectron distributions, providing a sensitive test of their validity. Finally, application of the determined matrix elements to ionization via more complex, polarization-shaped, pulses is demonstrated, illustrating the utility of this methodology towards detailed understanding of complex ionization control schemes and suggesting the utility of such "multiplexed" intrapulse processes as powerful tools for measurement. PMID:24949763

  9. 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.

  10. Hybrid Gaussian-discrete-variable representation approach to molecular continuum processes: Application to photoionization of diatomic Li2+

    NASA Astrophysics Data System (ADS)

    Yip, F. L.; McCurdy, C. W.; Rescigno, T. 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 and discrete-variable representation functions. This combined basis is applied to calculate single photoionization cross sections for molecular Li2+ , which has a large equilibrium bond distance (R=5.86a0) . The highly nonspherical nature of Li2+ 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.

  11. 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.

  12. 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.

  13. Photoelectronic characterization of heterointerfaces.

    SciTech Connect

    Brumbach, Michael Todd

    2012-02-01

    In many devices such as solar cells, light emitting diodes, transistors, etc., the performance relies on the electronic structure at interfaces between materials within the device. The objective of this work was to perform robust characterization of hybrid (organic/inorganic) interfaces by tailoring the interfacial region for photoelectron spectroscopy. Self-assembled monolayers (SAM) were utilized to induce dipoles of various magnitudes at the interface. Additionally, SAMs of molecules with varying dipolar characteristics were mixed into spatially organized structures to systematically vary the apparent work function. Polymer thin films were characterized by depositing films of varying thicknesses on numerous substrates with and without interfacial modifications. Hard X-ray photoelectron spectroscopy (HAXPES) was performed to evaluate a buried interface between indium tin oxide (ITO), treated under various conditions, and poly(3-hexylthiophene) (P3HT). Conducting polymer films were found to be sufficiently conducting such that no significant charge redistribution in the polymer films was observed. Consequently, a further departure from uniform substrates was taken whereby electrically disconnected regions of the substrate presented ideally insulating interfacial contacts. In order to accomplish this novel strategy, interdigitated electrodes were used as the substrate. Conducting fingers of one half of the electrodes were electrically grounded while the other set of electrodes were electronically floating. This allowed for the evaluation of substrate charging on photoelectron spectra (SCOPES) in the presence of overlying semiconducting thin films. Such an experiment has never before been reported. This concept was developed out of the previous experiments on interfacial modification and thin film depositions and presents new opportunities for understanding chemical and electronic changes in a multitude of materials and interfaces.

  14. Attosecond photoionization dynamics with stimulated core-valence transitions

    NASA Astrophysics Data System (ADS)

    You, Jhih-An; Rohringer, Nina; Dahlström, Jan Marcus

    2016-03-01

    We investigate ionization of neon atoms by an isolated attosecond pump pulse in the presence of two coherent extreme ultraviolet or x-ray probe fields. The probe fields are tuned to a core-valence transition in the residual ion and induce spectral shearing of the photoelectron distributions. We show that the photoelectron-ion coincidence signal contains an interference pattern that depends on the temporal structure of the attosecond pump pulse and the stimulated core-valence transition. Many-body perturbation theory is used to compute "atomic response times" for the processes and we find strikingly different behavior for stimulation to the outer-core hole (2 p ↔2 s ) and stimulation to the inner-core hole (2 p ↔1 s ). The response time of the inner-core transition is found to be comparable to that of state-of-the-art laser-based characterization techniques for attosecond pulses.

  15. Off-resonance photoemission dynamics studied by recoil frame F1s and C1s photoelectron angular distributions of CH{sub 3}F

    SciTech Connect

    Stener, M. Decleva, P.; Mizuno, T.; Yagishita, A.; Yoshida, H.

    2014-01-28

    F1s and C1s photoelectron angular distributions are considered for CH{sub 3}F, a molecule which does not support any shape resonance. In spite of the absence of features in the photoionization cross section profile, the recoil frame photoelectron angular distributions (RFPADs) exhibits dramatic changes depending on both the photoelectron energy and polarization geometry. Time-dependent density functional theory calculations are also given to rationalize the photoionization dynamics. The RFPADs have been compared with the theoretical calculations, in order to assess the accuracy of the theoretical method and rationalize the experimental findings. The effect of finite acceptance angles for both ionic fragments and photoelectrons has been included in the calculations, as well as the effect of rotational averaging around the fragmentation axis. Excellent agreement between theory and experiment is obtained, confirming the good quality of the calculated dynamical quantities (dipole moments and phase shifts)

  16. Photoionized astrophysical plasmas in the laboratory

    SciTech Connect

    Hill, Edward; Rose, Steven

    2010-10-15

    The time-dependent collisional-radiative code ALICE [E. G. Hill and S. J. Rose, High Energy Density Phys. 5, 302 (2009)] is used to model the spectrum from a laboratory photoionized silicon plasma [S. Fujioka et al., Nat. Phys. 5, 821 (2009)]. The results show a good agreement with the laboratory spectrum and lend support to the accompanying analytical discussion of photoionized laboratory spectra, their parametrization, and relevance to astrophysics.

  17. 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.

  18. 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.

  19. Satellite structure in the Argon 1s photoelectron spectrum

    SciTech Connect

    Azuma, Y.; LeBrun, T.; MacDonald, M.; Southworth, S.H.

    1995-08-01

    Atomic inner-shell photoelectron spectra typically display several relatively weak {open_quotes}satellite peaks{close_quotes} at higher ionization energy than the primary peak. Such satellite peaks are associated with final-state configurations corresponding to ionization of an inner-shell electron and excitation or ionization of one or more valence electrons. The observation of satellite peaks demonstrates that the independent-electron picture is inadequate to describe atomic structure and the photoionization process. The measured energies and intensities of photoelectron satellites provide sensitive tests of many-electron theoretical models. We recorded the Ar 1s photoelectron spectrum on beam line X-24A at an X-ray energy of 3628 eV. The primary peak at 3206 eV ionization energy was recorded at an observed resolution of 1.8 eV (FWHM). The satellite structure shows remarkable similarity to that recorded in the suprathreshold region of the Ar K photoabsorption cross section, demonstrating the manner in which these techniques complement each other. Surprisingly, while the region just above the K threshold in Ar was the subject of several theoretical studies using multi-configuration calculations, we find good agreement between our results and those of Dyall and collaborators using a shake model.

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

    NASA Astrophysics Data System (ADS)

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

    2009-03-01

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

  1. 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

  2. The 2p photoionization of ground-state sodium in the vicinity of Cooper minima

    NASA Astrophysics Data System (ADS)

    Liu, Xiaobin; Shi, Yinglong; Dong, Chenzhong

    2016-07-01

    The photoionization processes of ground-state sodium have been investigated with the multiconfiguration Dirac–Fock method. The results are in good or at least reasonable agreement with available experimental and theoretical data. In the energy region near the threshold, the cross sections show non-monotonic changes because of Cooper minima, which due to the sign changes of dominant dipole matrix elements and are very sensitive to electron correlations. As the energy increases continuously, the radial wave functions of the photoelectrons will move towards the nucleus. The values of the cross sections, and hence the Cooper minima, mainly depend on the relative positions of the one-electron radial wave functions of the initial bound electrons 2{p}1/{2,3/2} and the continuum photoelectrons.

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

    DOE PAGESBeta

    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, 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

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

    NASA Astrophysics Data System (ADS)

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

    2016-03-01

    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.

  5. Modeling photoionization of aqueous DNA and its components.

    PubMed

    Pluhařová, Eva; Slavíček, Petr; Jungwirth, Pavel

    2015-05-19

    Radiation damage to DNA is usually considered in terms of UVA and UVB radiation. These ultraviolet rays, which are part of the solar spectrum, can indeed cause chemical lesions in DNA, triggered by photoexcitation particularly in the UVB range. Damage can, however, be also caused by higher energy radiation, which can ionize directly the DNA or its immediate surroundings, leading to indirect damage. Thanks to absorption in the atmosphere, the intensity of such ionizing radiation is negligible in the solar spectrum at the surface of Earth. Nevertheless, such an ionizing scenario can become dangerously plausible for astronauts or flight personnel, as well as for persons present at nuclear power plant accidents. On the beneficial side, ionizing radiation is employed as means for destroying the DNA of cancer cells during radiation therapy. Quantitative information about ionization of DNA and its components is important not only for DNA radiation damage, but also for understanding redox properties of DNA in redox sensing or labeling, as well as charge migration along the double helix in nanoelectronics applications. Until recently, the vast majority of experimental and computational data on DNA ionization was pertinent to its components in the gas phase, which is far from its native aqueous environment. The situation has, however, changed for the better due to the advent of photoelectron spectroscopy in liquid microjets and its most recent application to photoionization of aqueous nucleosides, nucleotides, and larger DNA fragments. Here, we present a consistent and efficient computational methodology, which allows to accurately evaluate ionization energies and model photoelectron spectra of aqueous DNA and its individual components. After careful benchmarking, the method based on density functional theory and its time-dependent variant with properly chosen hybrid functionals and polarizable continuum solvent model provides ionization energies with accuracy of 0.2-0.3 e

  6. Molecular-frame photoelectron angular distributions Molecular-frame photoelectron angular distributions

    NASA Astrophysics Data System (ADS)

    Lucchese, Robert R.; Stolow, Albert

    2012-10-01

    Angle-resolved photoelectron measurements in molecular ionization continue to grow in importance due to their sensitivity to molecular dynamics combined with their avoidance of deleterious averaging over molecular orientation. This special issue contains only regularly refereed articles and provides an account of current experimental and theoretical studies of such molecular-frame photoelectron angular distributions (MFPADs). Recent experimental activity in this field has been stimulated by advances in light sources such as x-ray free electron lasers, attosecond XUV laser pulses and phase-stable ultrashort strong laser fields. This effort is further amplified by recent developments in coincidence detection and molecular-frame alignment/orientation techniques. Beyond perturbative light-matter interactions, strong field processes such as tunnel ionization, above threshold ionization and rescattering phenomena such as high harmonic generation and laser-induced electron diffraction are beginning to probe molecular-frame photoelectron-molecule scattering dynamics. Theoretical developments are playing an equally important role in furthering molecular-frame photoelectron science. This issue contains several purely theoretical papers that aim to provide insight into possible schemes for using MFPADs in the study of molecular dynamics. Because the details of the electron-molecule scattering dynamics are important to the interpretation of experimental data, significant progress is made by a close collaboration between theory and experiment. There are a number of such contributions in this issue that combine theory and experiment to obtain a detailed understanding of the observed processes. One recurring theme is the use of measured MFPADs as probes of the molecular state and to uncover information about the dynamics of molecular systems. Contributions in this issue consider using MFPADs to investigate molecular geometry or the rotational, vibrational or electronic state of a

  7. Photoionization cross section for He in the hyperspherical coordinate method

    SciTech Connect

    Miller, D.L.; Starace, A.F.

    1980-01-01

    In order to more fully explore the role of electron correlations in the photoionization process the hyperspherical coordinate method of Macek was employed in calculating photoionization cross sections of He. Results are presented and discussed. (WHK)

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

    NASA Astrophysics Data System (ADS)

    Braunstein, Matthew

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

  9. Atomic Auger Doppler effects upon emission of fast photoelectrons.

    PubMed

    Simon, Marc; Püttner, Ralph; Marchenko, Tatiana; Guillemin, Renaud; Kushawaha, Rajesh K; Journel, Loïc; Goldsztejn, Gildas; Piancastelli, Maria Novella; Ablett, James M; Rueff, Jean-Pascal; Céolin, Denis

    2014-01-01

    Studies of photoemission processes induced by hard X-rays including production of energetic electrons have become feasible due to recent substantial improvement of instrumentation. Novel dynamical phenomena have become possible to investigate in this new regime. Here we show a significant change in Auger emission following 1s photoionization of neon, which we attribute to the recoil of the Ne ion induced by the emission of a fast photoelectron. Because of the preferential motion of the ionized Ne atoms along two opposite directions, an Auger Doppler shift is revealed, which manifests itself as a gradual broadening and doubling of the Auger spectral features. This Auger Doppler effect should be a general phenomenon in high-energy photoemission of both isolated atoms and molecules, which will have to be taken into account in studies of other recoil effects such as vibrational or rotational recoil in molecules, and may also have consequences in measurements in solids. PMID:24906107

  10. Photodissociation and photoionization of organosulfur radicals

    SciTech Connect

    Hsu, Chia-Wei

    1994-05-27

    The dynamics of S({sup 3}P{sub 2,1,0}, {sup 1}D{sub 2}) production from the 193 nm photodissociation of CH{sub 3}SCH{sub 3}, H{sub 2}S and CH{sub 3}SH have been studied using 2 + 1 resonance-enhanced multiphoton ionization (REMPI) techniques. The 193 nm photodissociation cross sections for the formation of S from CH{sub 3}S and HS initially prepared in the photodissociation of CH{sub 3}SCH{sub 3} and H{sub 2}S are estimated to be 1 {times} 10{sup {minus}18} and 1.1 {times} 10{sup {minus}18} cm{sup 2}, respectively. The dominant product from CH{sub 3}S is S({sup 1}D), while that from SH is S({sup 3}P). Possible potential energy surfaces involved in the 193 nm photodissociation of CH{sub 3}S({tilde X}) and SH(X) have been also examined. Threshold photoelectron (PE) spectra for SH and CH{sub 3}S formed in the ultraviolet photodissociation of H{sub 2}S and CH{sub 3}SH, 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 {Delta}N < 0 with the {Delta}N value up to {minus}3, an observation similar to that found in the PFI-PE spectra of OH (OD) and NO. The ionization energies for SH(X{sup 2}{product}{sub 3,2}) and CH{sub 3}S({tilde X}{sup 2}E{sub 3/2}) are determined to be 84,057.5 {plus_minus} 3 cm{sup {minus}1} and 74,726 {plus_minus} 8 cm{sup {minus}1} respectively. The spin-orbit splittings for SH(X{sup 2}{product}{sub 3/2,1/2}) and CH{sub 3}S({tilde X}{sup 2}E{sub 3/2,1/2}) are found to be 377 {plus_minus} 2 and 257 {plus_minus} 5 cm{sup {minus}1}, respectively, in agreement with previous measurements. The C-S stretching frequency for CH{sub 3}S{sup +}({tilde X}{sup 3}A{sub 2}) is 733 {plus_minus} 5 cm{sup {minus}1}. This study illustrates that the PFI-PE detection method can be a sensitive probe for the nascent internal energy distribution of photoproducts.

  11. Decomposition of diazomeldrum's acid: a threshold photoelectron spectroscopy study.

    PubMed

    Lang, Melanie; Holzmeier, Fabian; Fischer, Ingo; Hemberger, Patrick

    2014-11-26

    Derivatives of meldrum's acid are known precursors for a number of reactive intermediates. Therefore, we investigate diazomeldrum's acid (DMA) and its pyrolysis products by photoionization using vacuum ultraviolet (VUV) synchrotron radiation. The threshold photoelectron spectrum of DMA yields an ionization energy (IE) of 9.68 eV. Several channels for dissociative photoionization are observed. The first one is associated with loss of CH3, leading to a daughter ion with m/z = 155. Its appearance energy AE0K was determined to be 10.65 eV by fitting the experimental data using statistical theory. A second parallel channel leads to m/z = 69, corresponding to N2CHCO, with an AE0K of 10.72 eV. Several other channels open up at higher energy, among them the formation of acetone cation, a channel expected to be the result of a Wolff-rearrangement (WR) in the cation. When diazomeldrum's acid is heated in a pyrolysis reactor, three thermal decomposition pathways are observed. The major one is well-known and yields acetone, N2 and CO as consequence of the WR. However, two further channels were identified: The formation of 2-diazoethenone, NNCCO, together with acetone and CO2 as the second channel and E-formylketene (OCCHCHCO), propyne, N2 and O2 as a third one. 2-Diazoethenone and E-formylketene were identified based on their threshold photoelectron spectra and accurate ionization energies could be determined. Ionization energies for several isomers of both molecules were also computed. One of the key findings of this study is that acetone is observed upon decomposition of DMA in the neutral as well as in the ion and both point to a Wolff rearrangement to occur. However, the ion is subject to other decomposition channels favored at lower internal energies. PMID:25369422

  12. Effects of anisotropic electron-ion interactions in atomic photoelectron angular distributions

    NASA Technical Reports Server (NTRS)

    Dill, D.; Starace, A. F.; Manson, S. T.

    1974-01-01

    The photoelectron asymmetry parameter beta in LS-coupling is obtained as an expansion into contributions from alternative angular momentum transfers j sub t. The physical significance of this expansion of beta is shown to be that: (1) the electric dipole interaction transfers to the atom a charcteristic single angular momentum j sub t = sub o, where sub o is the photoelectron's initial orbital momentum; and (2) angular momentum transfers indicate the presence of anisotropic interaction of the outgoing photoelectron with the residual ion. For open shell atoms the photoelectron-ion interaction is generally anisotropic; photoelectron phase shifts and electric dipole matrix elements depend on both the multiplet term of the residual ion and the total orbital momentum of the ion-photoelectron final state channel. Consequently beta depends on the term levels of the residual ion and contains contributions from all allowed values of j sub t. Numerical calculations of the asymmetry parameters and partial cross sections for photoionization of atomic sulfur are presented.

  13. Effect of strongly coupled plasma on photoionization cross section

    NASA Astrophysics Data System (ADS)

    Das, Madhusmita

    2014-01-01

    The effect of strongly coupled plasma on the ground state photoionization cross section is studied. In the non relativistic dipole approximation, cross section is evaluated from bound-free transition matrix element. The bound and free state wave functions are obtained by solving the radial Schrodinger equation with appropriate plasma potential. We have used ion sphere potential (ISP) to incorporate the plasma effects in atomic structure calculation. This potential includes the effect of static plasma screening on nuclear charge as well as the effect of confinement due to the neighbouring ions. With ISP, the radial equation is solved using Shooting method approach for hydrogen like ions (Li+2, C+5, Al+12) and lithium like ions (C+3, O+5). The effect of strong screening and confinement is manifested as confinement resonances near the ionization threshold for both kinds of ions. The confinement resonances are very much dependent on the edge of the confining potential and die out as the plasma density is increased. Plasma effect also results in appearance of Cooper minimum in lithium like ions, which was not present in case of free lithium like ions. With increasing density the position of Cooper minimum shifts towards higher photoelectron energy. The same behaviour is also true for weakly coupled plasma where plasma effect is modelled by Debye-Huckel potential.

  14. Effect of strongly coupled plasma on photoionization cross section

    SciTech Connect

    Das, Madhusmita

    2014-01-15

    The effect of strongly coupled plasma on the ground state photoionization cross section is studied. In the non relativistic dipole approximation, cross section is evaluated from bound-free transition matrix element. The bound and free state wave functions are obtained by solving the radial Schrodinger equation with appropriate plasma potential. We have used ion sphere potential (ISP) to incorporate the plasma effects in atomic structure calculation. This potential includes the effect of static plasma screening on nuclear charge as well as the effect of confinement due to the neighbouring ions. With ISP, the radial equation is solved using Shooting method approach for hydrogen like ions (Li{sup +2}, C{sup +5}, Al{sup +12}) and lithium like ions (C{sup +3}, O{sup +5}). The effect of strong screening and confinement is manifested as confinement resonances near the ionization threshold for both kinds of ions. The confinement resonances are very much dependent on the edge of the confining potential and die out as the plasma density is increased. Plasma effect also results in appearance of Cooper minimum in lithium like ions, which was not present in case of free lithium like ions. With increasing density the position of Cooper minimum shifts towards higher photoelectron energy. The same behaviour is also true for weakly coupled plasma where plasma effect is modelled by Debye-Huckel potential.

  15. Branching ratio deviations from statistical behavior in core photoionization

    NASA Astrophysics Data System (ADS)

    Di Tommaso, Devis; Decleva, Piero

    2005-08-01

    Accurate calculations of carbon 1s photoionization cross sections have been performed at the density functional level with the B-spline linear combination of atomic orbitals approach. The molecules considered are FCCH, FCCCH3, FCCCN, F2CCH2, CF3COOCH2CH3, and C3H5O. The variation of the branching ratios relative to inequivalent C 1s ionizations have been evaluated from threshold to about 100 eV photoelectron kinetic energy. Large deviations from the statistical ratios are observed at low energies, which remain often significant several tens of eV above threshold. The importance of taking into account core branching ratios for peak deconvolution and quantitative analysis, as well as an additional tool for structural information, is pointed out. Strong shape resonant effects are found to largely cancel in branching ratios. Their nature and variation along the series is analyzed in the framework of excitations into σ* valence orbitals.

  16. Valence Auger decay following 3 s photoionization in potassium

    NASA Astrophysics Data System (ADS)

    Palaudoux, J.; Sheinerman, S.; Soronen, J.; Huttula, S.-M.; Huttula, M.; Jänkälä, K.; Andric, L.; Ito, K.; Lablanquie, P.; Penent, F.; Bizau, J.-M.; Guilbaud, S.; Cubaynes, D.

    2015-07-01

    We have studied photoionization in the inner valence 3 s subshell of K and the spectroscopic properties of the two 3 s-1(1S) and (3S) resulting states. Similar to the Rb and Cs cases, the lifetime widths of the (1S) and (3S) states are found to be markedly different, due to the electron correlation effects. The main part of the study deals with the subsequent Auger decay of the 3 s-1 states, which have the particularity to involve low energy (˜5 eV ) Auger electrons. A magnetic bottle spectrometer with a multicoincidence technique has been used to observe and filter the Auger spectra with respect to the K2 + final state. The evolution of these Auger spectra has been investigated near the ionization threshold. They show strong post-collision interaction (PCI) effects, which are well reproduced by semiclassical and eikonal models. They reveal the importance of the photoelectron-Auger-electron interaction associated with these low energy Auger electrons.

  17. The nonresonant two-photon zero kinetic energy photoelectron spectrum from the electronic ground state of H2S

    NASA Astrophysics Data System (ADS)

    Fischer, Ingo; Lochschmidt, Andreas; Strobel, Andreas; Niedner-Schatteburg, Gereon; Mueller-Dethlefs, Klaus; Bondybey, Vladimir E.

    1993-03-01

    Zero kinetic energy photoelectron spectra from the electronic ground state of hydrogen sulfide are obtained via nonresonant two-photon ionization with complete rotational resolution in the ion. The two-photon spectra are compared with those recently obtained via one-photon VUV photoionization. The spectra show a close similarity, but type a transitions in the two-photon spectra are twice as intense.

  18. 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.

  19. A two-color infrared-vacuum ultraviolet laser pulsed field ionization photoelectron study of NH3.

    PubMed

    Bahng, Mi-Kyung; Xing, Xi; Baek, Sun Jong; Ng, C Y

    2005-08-22

    We have observed fully rotationally resolved transitions of the photoelectron vibrational bands 2(4), 2(5), 1(1)2(1), and 1(1)2(3) for ammonia cation (NH3+) by two-color infrared (IR)-vacuum ultraviolet (VUV)- pulsed field-ionization photoelectron (PFI-PE) measurements. By preparing an intermediate rovibrational state of neutral NH(3) with a known parity by IR excitation followed by VUV-PFI-PE measurements, we show that the photoelectron parity can be determined unambiguously. The IR-VUV-PFI-PE measurement of the 2(4) band clearly reveals the formation of both even and odd l states for the photoelectrons, where l is the orbital angular momentum quantum number. This observation is consistent with the conclusion that the lack of inversion symmetry for NH3 and NH3+ allows odd/even l mixings, rendering the production of both odd and even l states for the photoelectrons. Evidence is also found, indicating that the photoionization transitions with DeltaK=0 are strongly favored compared to that with DeltaK=3. For the 2(5), 1(1)2(1), and 1(1)2(3) bands, only DeltaK=0 transitions for the production of even l photoelectron states from the J'K'=2(0) rotational level of NH3(nu1=1) are observed. The preferential formation of even l photoelectron states for these vibrational bands is attributed to the fact that the DeltaK=0 transitions for the formation of odd l photoelectron states from the 2(0) rotational level of NH3(nu1=1) are suppressed by the constraint of nuclear-spin statistics. In addition to information obtained on the photoionization dynamics of NH3, this experiment also provides a more precise value of 3232+/-10 cm-1 for the nu1+ (N-H stretch) vibrational frequency of NH3+. PMID:16164295

  20. Photoelectron recapture and reemission process associated with double Auger decay in Ar

    NASA Astrophysics Data System (ADS)

    Hikosaka, Y.; Mashiko, R.; Odagiri, T.; Adachi, J.; Tanaka, H.; Kosuge, T.; Ito, K.

    2016-06-01

    Multielectron coincidence spectroscopy has been performed for Ar at a photon energy of only 0.2 eV above the 2 p1 /2 threshold. It is revealed that a postcollision interaction induced by double Auger decay leads to photoelectron recapture, followed by reemission of the captured electron, where the recapture of the slow photoelectron forms the A r2 + Rydberg-excited states which subsequently undergo autoionization. The energy correlation of the emitted electrons discloses that both direct and cascade paths in the double Auger decay contribute to the photoelectron recapture.

  1. Simulation of time resolved photoelectron spectra with Stieltjes imaging illustrated on ultrafast internal conversion in pyrazine

    NASA Astrophysics Data System (ADS)

    Werner, Ute; Mitrić, Roland; Bonačić-Koutecký, Vlasta

    2010-05-01

    We present an approach for the simulation of time resolved photoelectron spectra based on the combination of the ab initio nonadiabatic molecular dynamics "on the fly" with the Stieltjes imaging method utilizing discrete neutral states above the ionization limit for the approximate description of the ionization continuum. Our approach has been implemented in the framework of the time-dependent density functional theory and has been applied to interrogate the ultrafast internal conversion between the S2 and S1 states in pyrazine. The simulations reveal that, parallel to the S2→S1 internal conversion, a change in the dominant ionization process (S2→D1 versus S1→D0) occurs on the time scale of 20 fs such that no significant change in the photoelectron kinetic energy distribution is observed. The presented results are in full agreement with the experimental results presented in the accompanying paper [Suzuki et al., J. Chem. Phys. 132, 174302 (2010)] and provide an insight into the interplay between the nonradiative relaxation and the photoionization process in pyrazine as reflected in the time resolved photoelectron spectrum. Our approach represents a general tool for the investigation of ultrafast photoionization processes in complex systems and thus can be used to investigate the ultrafast femtochemistry of complex molecular systems including all degrees of freedom.

  2. Relative measurement of the photoionization cross section of the 7D5/2 state of cesium

    NASA Astrophysics Data System (ADS)

    Armstrong, D. J.; Westling, L. A.; Smith, S. J.

    1991-06-01

    We have carried out a relative measurement of the total photoionization cross section of the excited 7D5/2 state of cesium for photoelectron energies in the range 0.103-0.127 Ry above the ionization threshold. Separate measurements were made using two different combinations of laser sources to populate and photoionize the 7D5/2 state. The first measurement was made with a cw diode laser and two pulsed dye lasers, while the second was made with three pulsed dye lasers. The measured cross section was found to vary slowly within experimental uncertainty over this energy range but was otherwise featureless. This result disagrees with the cross section predicted by a Hartree-Slater calculation [J. Lahiri and S. T. Manson, Phys. Rev. A 33, 3151 (1986)], which displayed a deep minimum in this spectral region.

  3. Vibrational branching ratios and asymmetry parameters in the photoionization of CO2 in the region between 650 Å and 840 Å

    National Institute of Standards and Technology Data Gateway

    SRD 119 Vibrational branching ratios and asymmetry parameters in the photoionization of CO2 in the region between 650 Å and 840 Å (Web, free access)   CO2 is studied using dispersed synchrotron radiation in the 650 Å to 850 Å spectral region. The vibrationally resolved photoelectron spectra are analyzed to generate relative vibrational transition amplitudes and the angular asymmetry parameters describing the various transitions observed.

  4. Versatile cluster based photoelectron spectrometer

    SciTech Connect

    Knappenberger, K. L. Jr.; Jones, C. E. Jr.; Sobhy, M. A.; Castleman, A. W. Jr.

    2006-12-15

    A recently constructed cluster based photoelectron spectrometer is described. This instrumentation is unique in that it enables the kinetic energy analysis of electrons ejected from both anions and neutral clusters. This capability permits the investigation of discrete electronic levels in all charge states (anionic, neutral, and cationic). A laser vaporization plasma reactor cluster source affixed with a sublimation cell is employed to produce a variety of metal clusters, and the resulting cluster distributions are analyzed with time-of-flight mass spectrometry. The corresponding electronic structure is analyzed with a 'magnetic bottle' photoelectron spectrometer. Examples of instrument performance operating in both anion photodetachment and neutral multiphoton ionization (MPI) modes are provided. In the case of neutral MPI, the corresponding product distribution is collected with a Wiley-McLaren [Rev. Sci. Instrum. 26, 1150 (1955)] mass spectrometer mounted perpendicular to the magnetic bottle photoelectron spectrometer.

  5. Molecular photoelectron angular distributions with intense attosecond circularly polarized UV laser pulses

    NASA Astrophysics Data System (ADS)

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

    2014-01-01

    We investigate effects of intermediate resonant electronic states on molecular photoelectron angular distributions (MPADs) by intense circularly polarized attosecond UV laser pulses. Simulations are performed on aligned H2+ by numerically solving the corresponding three dimensional time dependent Schrödinger equations. MPADs exhibit signature of rotations, which is shown to be critically sensitive to the symmetry of the intermediate resonant electronic state and the pulse intensity. This sensitivity is attributed to the coherent population transfer in the initial and intermediate resonant states, thus suggesting a method to control molecular photoionization on attosecond time scale.

  6. Molecular photoelectron momentum distributions by intense orthogonally polarized attosecond ultraviolet laser pulses

    NASA Astrophysics Data System (ADS)

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

    2015-10-01

    We study molecular photoelectron momentum distributions (MPMDs) of aligned H2+ by intense orthogonally polarized attosecond ultraviolet laser pulses. Photoionization is simulated by numerically solving corresponding three-dimensional time dependent Schrödinger equations with static nuclei. It is found that altering pulse phases ϕ varies the structure of MPMDs, which is attributed to the interference effect between orthogonal polarization ionizations. The phase ϕ dependent MPMDs are also a function of molecular alignment and pulse wavelengths. Altering the symmetry of initial electronic states offers the possibility of imaging molecular orbitals by orthogonal polarization attosecond MPMDs.

  7. Photoelectron angular distributions in negative-ion photodetachment from mixed sp states.

    PubMed

    Grumbling, Emily R; Sanov, Andrei

    2011-10-28

    We describe an approach for constructing analytical models for the energy-dependence of photoelectron angular distributions in the one-electron, non-relativistic approximation. We construct such a model for electron emission from an orbital described as a superposition of s- and p-type functions, using linearly polarized light. In the limits of pure s or pure p electron photodetachment or photoionization, the model correctly reproduces the familiar Cooper-Zare formula. The model predictions are compared to experimental results for strongly solvated H(-) and NH(2)(-), corresponding to predominantly s and predominantly p character parent states, respectively. PMID:22047234

  8. Photoelectron angular distributions in negative-ion photodetachment from mixed sp states

    NASA Astrophysics Data System (ADS)

    Grumbling, Emily R.; Sanov, Andrei

    2011-10-01

    We describe an approach for constructing analytical models for the energy-dependence of photoelectron angular distributions in the one-electron, non-relativistic approximation. We construct such a model for electron emission from an orbital described as a superposition of s- and p-type functions, using linearly polarized light. In the limits of pure s or pure p electron photodetachment or photoionization, the model correctly reproduces the familiar Cooper-Zare formula. The model predictions are compared to experimental results for strongly solvated H- and NH2-, corresponding to predominantly s and predominantly p character parent states, respectively.

  9. Calculation of Ar photoelectron satellites in the hard-x-ray region

    NASA Astrophysics Data System (ADS)

    Yarzhemsky, V. G.; Amusia, M. Ya.

    2016-06-01

    The intensities of photoelectron satellite lines, corresponding to the double core hole (DCH) states of Ar 1 s ionization by hard x rays, are calculated using the many-body perturbation theory. Calculations support the interpretation of the most intense lines as the shake-up excitations 2 p →4 p . It is demonstrated that the intensities of the spectrum lines corresponding to 4 s (and 3 d ) excited states in the DCH field can be explained only taking into account the knock-up process 2 p →3 d along with the shake-up process 1 s →4 s that accompanies 2 p photoionization.

  10. Single and double photoionization of lithium

    NASA Astrophysics Data System (ADS)

    Huang, M.-T.; Wehlitz, R.; Azuma, Y.; Pibida, L.; Sellin, I. A.; Cooper, J. W.; Koide, M.; Ishijima, H.; Nagata, T.

    1999-05-01

    The photoion Li2+/Li+ production cross section ratio of ground-state atomic lithium has been measured for photon energies ranging from 80 to 424 eV. The absolute cross sections for the Li2+ and Li+ yield are also derived. In this energy region, the Li2+/Li+ ratio reaches a plateau of about 1.0% before reaching a maximum of about 4.5%, then decreases slowly. Good agreement is found between the measured total photoionization cross sections of lithium and theoretical calculations. The Li2+/Li+ ratio is also compared to the He2+/He+ ratio from excited He(1s2s) for photon energies up to 70 eV above threshold. The branching ratio of Li2+ to total Li ion production is also compared to the single-ionization cross section of electron impact on Li+ ions.

  11. Scheme for multistep resonance photoionization of atoms

    NASA Astrophysics Data System (ADS)

    Liu, Bo; Ning, Xi-Jing

    2001-07-01

    Traditional schemes for multistep resonance photoionization of atoms let every employed laser beam interact with the atoms simultaneously. In such a situation, analyses via time-dependent Schrödinger equation show that high ionization probability requires all the laser beams must be intense enough. In order to decrease laser intensity, we proposed a scheme that the laser beam used to pump the excited atoms (in a higher bound state) into an autoionization state does not interact with the atoms until all the population is transferred by the other lasers from a ground state to the bound state. As an interesting example, we examined three-step photoionization of 235U with our scheme, showing that the intensity of two laser beams can be lowered by two orders of magnitude without losing high ionization probability.

  12. Photoabsorbtion and Photoionization of Diatomic Molecules

    NASA Astrophysics Data System (ADS)

    Saenz, Alejandro; Dumitriu, Irina

    2008-05-01

    The photodissociation spectra of HeH^+ will be presented together with photoionization cross sections of the alkali dimer cations Li^+2, Na^+2, and LiNa^+. The latter have been calculated using two methods: a time-independent perturbative method and a time-dependent non-perturbative one. The photodissociation of HeH^+ which is of interest for astrophysics and the tritium neutrino-mass experiments currently draws special attention because of the newly developed FEL experimental set-up FLASH in Hamburg at which dissociation of HeH^+ by VUV radiation has been investigated [Phys. Rev. Lett. 98, 223202 (2007)]. The alkali dimer cations are presented as a first methodological step to the photoionization of the alkali dimers, but they are also interesting by themselves since no ab initio data were available for the continuum spectra.

  13. The design of double electrostatic-lens optics for resonance enhanced multiphoton ionization and photoelectron imaging experiments

    NASA Astrophysics Data System (ADS)

    Qu, Zehua; Li, Chunsheng; Qin, Zhengbo; Zheng, Xianfeng; Yao, Guanxin; Zhang, Xianyi; Cui, Zhifeng

    2015-06-01

    Compared to single ion/electron-optics for velocity-map imaging, a double-focusing lens assembly designed not only allows for mapping velocity imaging of photoelectrons but also allows for investigating the vibrational structure of the intermediate states of neutral species in resonance enhanced multiphoton ionization (REMPI) spectra. In this presentation, in order to record REMPI and photoelectron spectra separately, we have constructed a compact photoelectron velocity-map imaging (VMI) apparatus combined with an opposite linear Wiley-Mclaren time-of-flight mass spectrometer (TOFMS). A mass resolution (m/Δm) of ˜1300 for TOFMS and electron energy resolution (ΔE/E) of 2.4% for VMI have been achieved upon three-photon ionization of Xe atom at 258.00 nm laser wavelength. As a benchmark, in combination of one-color (1 + 1) REMPI and photoelectron imaging of benzene via 61 and 6111 vibronic levels in the S1 state, the vibrational structures of the cation and photoelectron angular anisotropy are unraveled. In addition, two-color (1 + 1') REMPI and photoelectron imaging of aniline was used to complete the accurate measurement of ionization potential (62 271 ± 3 cm-1). The results suggest that the apparatus is a powerful tool for studying photoionization dynamics in the photoelectron imaging using vibrational-state selected excitation to the intermediate states of neutrals based on REMPI technique.

  14. The design of double electrostatic-lens optics for resonance enhanced multiphoton ionization and photoelectron imaging experiments

    SciTech Connect

    Qu, Zehua; Li, Chunsheng; Qin, Zhengbo E-mail: xfzheng@mail.ahnu.edu.cn; Zheng, Xianfeng E-mail: xfzheng@mail.ahnu.edu.cn; Yao, Guanxin; Zhang, Xianyi; Cui, Zhifeng

    2015-06-15

    Compared to single ion/electron-optics for velocity-map imaging, a double-focusing lens assembly designed not only allows for mapping velocity imaging of photoelectrons but also allows for investigating the vibrational structure of the intermediate states of neutral species in resonance enhanced multiphoton ionization (REMPI) spectra. In this presentation, in order to record REMPI and photoelectron spectra separately, we have constructed a compact photoelectron velocity-map imaging (VMI) apparatus combined with an opposite linear Wiley-Mclaren time-of-flight mass spectrometer (TOFMS). A mass resolution (m/Δm) of ∼1300 for TOFMS and electron energy resolution (ΔE/E) of 2.4% for VMI have been achieved upon three-photon ionization of Xe atom at 258.00 nm laser wavelength. As a benchmark, in combination of one-color (1 + 1) REMPI and photoelectron imaging of benzene via 6{sup 1} and 6{sup 1}1{sup 1} vibronic levels in the S{sub 1} state, the vibrational structures of the cation and photoelectron angular anisotropy are unraveled. In addition, two-color (1 + 1′) REMPI and photoelectron imaging of aniline was used to complete the accurate measurement of ionization potential (62 271 ± 3 cm{sup −1}). The results suggest that the apparatus is a powerful tool for studying photoionization dynamics in the photoelectron imaging using vibrational-state selected excitation to the intermediate states of neutrals based on REMPI technique.

  15. The design of double electrostatic-lens optics for resonance enhanced multiphoton ionization and photoelectron imaging experiments.

    PubMed

    Qu, Zehua; Li, Chunsheng; Qin, Zhengbo; Zheng, Xianfeng; Yao, Guanxin; Zhang, Xianyi; Cui, Zhifeng

    2015-06-01

    Compared to single ion/electron-optics for velocity-map imaging, a double-focusing lens assembly designed not only allows for mapping velocity imaging of photoelectrons but also allows for investigating the vibrational structure of the intermediate states of neutral species in resonance enhanced multiphoton ionization (REMPI) spectra. In this presentation, in order to record REMPI and photoelectron spectra separately, we have constructed a compact photoelectron velocity-map imaging (VMI) apparatus combined with an opposite linear Wiley-Mclaren time-of-flight mass spectrometer (TOFMS). A mass resolution (m/Δm) of ∼1300 for TOFMS and electron energy resolution (ΔE/E) of 2.4% for VMI have been achieved upon three-photon ionization of Xe atom at 258.00 nm laser wavelength. As a benchmark, in combination of one-color (1 + 1) REMPI and photoelectron imaging of benzene via 6(1) and 6(1)1(1) vibronic levels in the S1 state, the vibrational structures of the cation and photoelectron angular anisotropy are unraveled. In addition, two-color (1 + 1') REMPI and photoelectron imaging of aniline was used to complete the accurate measurement of ionization potential (62,271 ± 3 cm(-1)). The results suggest that the apparatus is a powerful tool for studying photoionization dynamics in the photoelectron imaging using vibrational-state selected excitation to the intermediate states of neutrals based on REMPI technique. PMID:26133827

  16. Photoionization and photodissociation in diffuse interstellar clouds

    SciTech Connect

    Roberge, W.G.; Dalgarno, A.; Flannery, B.P.

    1981-02-01

    An accurate treatment of radiative transfer is used to explore the effects of grain scattering properties on the photoionization and photodissociation efficiencies of atomic and molecular constituents in diffuse clouds and to calculate the rates of heat deposition by photoelectric emission from grains. The observational data on ionization and dissociation are consistent with, but do not establish, a grain scattering model which is highly anisotropic at short wavelengths.

  17. Absolute photoionization cross sections of atomic oxygen

    NASA Technical Reports Server (NTRS)

    Samson, J. A. R.; Pareek, P. N.

    1985-01-01

    The absolute values of photoionization cross sections of atomic oxygen were measured from the ionization threshold to 120 A. An auto-ionizing resonance belonging to the 2S2P4(4P)3P(3Do, 3So) transition was observed at 479.43 A and another line at 389.97 A. The experimental data is in excellent agreement with rigorous close-coupling calculations that include electron correlations in both the initial and final states.

  18. Absolute photoionization cross sections of atomic oxygen

    NASA Technical Reports Server (NTRS)

    Samson, J. A. R.; Pareek, P. N.

    1982-01-01

    The absolute values of photoionization cross sections of atomic oxygen were measured from the ionization threshold to 120 A. An auto-ionizing resonance belonging to the 2S2P4(4P)3P(3Do, 3So) transition was observed at 479.43 A and another line at 389.97 A. The experimental data is in excellent agreement with rigorous close-coupling calculations that include electron correlations in both the initial and final states.

  19. Photoionization models of the CALIFA HII regions

    NASA Astrophysics Data System (ADS)

    Morisset, C.; Delgado-Inglada, G.; Sánchez, S. F.

    2016-06-01

    We present here a short summary of a forthcoming paper on photoionization models based on CALIFA observations of HII regions. For each of the ˜ 20,000 sources of the CALIFA H ii regions catalog, a grid of photoionization models is computed assuming the ionizing SED being described by the underlying stellar population obtained from spectral synthesis modeling. The nebular metallicity (associated to O/H) is defined using the classical strong line method O3N2. The remaining free parameters are the abundance ratio N/O and the ionization parameter U, which are determined by looking for the model fitting [N II]/Hα and [O III]/Hβ. The models are also selected to fit [O II]/Hβ. This process leads to a set of ˜ 3,200 models that reproduce simultaneously the three observations. We determine new relations between the nebular parameters, like the ionization parameter U and the [O II]/[O III] or [S II]/[S III] line ratios. A new relation between N/O and O/H is obtained, mostly compatible with previous empirical determinations (and not with previous results obtained using photoionization models). A new relation between U and O/H is also determined. All the models are publicly available on the Mexican Millions Models database 3MdB.

  20. Structured photoionization continuum of superheated cesium vapor

    NASA Astrophysics Data System (ADS)

    Pichler, G.; Makdisi, Y.; Kokaj, J.; Thomas, N.; Mathew, J.

    2015-08-01

    We studied the absorption spectrum of dense cesium vapor in an all-sapphire cell with a special emphasis on the highly structured photoionization continuum. This continuum appears to be composed of atomic and molecular contributions which can be separated by means of additional superheating of the cesium vapor in the sapphire cell. This was possible due to the small amount of cesium filling which completely evaporated at a temperature of around 450 °C. This enabled the overheating of cesium dimers which greatly reduced its concentration at a temperature of 900 °C, leaving almost pure atomic Cs vapor. The analysis of the thermal destruction indicated that the highly structured molecular component of the photoionization continuum can be entirely attributed to cesium dimers. We discuss the possible origin of the structured photoionization continuum as stemming from the absorption process from the ground state of the Cs2 molecule to the doubly excited Cs2** molecule located above Cs2+ molecular ionization limit. The corresponding potential curves are subjected to mutual interactions and autoionization.

  1. Structured photoionization continuum of cesium vapor

    NASA Astrophysics Data System (ADS)

    Pichler, Goran; Makdisi, Yacoub; Kokaj, Jahja; Thomas, Nicky; Mathew, Joseph; AMIP Team

    2015-05-01

    We studied absorption spectrum of dense cesium vapor in an all-sapphire cell with a special emphasis on the highly structured photoionization continuum. This continuum appears to be composed of atomic and molecular contributions which can be separated by means of additional superheating of the sapphire cell. This was possible due to the small amount of cesium filling which completely evaporated at temperature of about 450 °C. This enabled the overheating of cesium dimers which almost disappeared at a temperature of 900 °C leaving pure atomic Cs vapor. The analysis of the thermal destruction indicated that the highly structured molecular component of the photoionization continuum can be entirely attributed to cesium dimers. We discuss the possible origin of the structured photoionization continuum as stemming from the absorption process from the ground Cs2 molecule to the doubly excited Cs2** molecule located above the molecular ionization limit Cs2+.The corresponding potential curves are subjected to a mutual interactions and autoionization.

  2. Multiple channel programmable coincidence counter

    DOEpatents

    Arnone, Gaetano J.

    1990-01-01

    A programmable digital coincidence counter having multiple channels and featuring minimal dead time. Neutron detectors supply electrical pulses to a synchronizing circuit which in turn inputs derandomized pulses to an adding circuit. A random access memory circuit connected as a programmable length shift register receives and shifts the sum of the pulses, and outputs to a serializer. A counter is input by the adding circuit and downcounted by the seralizer, one pulse at a time. The decoded contents of the counter after each decrement is output to scalers.

  3. Coincidence/Multiplicity Photofission Measurements

    SciTech Connect

    J.L. Jones; M.T. Swinhoe; S.J. Tobin; W. H. Geist; D.R. Norman; R.B. Rothrock; C.R. Freeman; K. J. Haskell

    2009-09-01

    An series of experiments using the Idaho National Laboratory (INL) photonuclear inspection system and a Los Alamos National Laboratory (LANL)-supplied, list-mode data acquisition method have shown enhanced performance utilizing pulsed photofission-induced, neutron coincidence counting between pulses of an up-to-10-MeV electron accelerator for nuclear material detection and identification. The enhanced inspection methodology has applicability to homeland security, treaty-related support, and weapon dismantlement applications. For the latter, this technology can directly support of Department of Energy/NA241 programmatic mission objectives relative to future Rocky Ridge-type testing campaigns for active inspection systems.

  4. Soft coincidence in late acceleration

    SciTech Connect

    Campo, Sergio del; Herrera, Ramon; Pavon, Diego

    2005-06-15

    We study the coincidence problem of late cosmic acceleration by assuming that the present ratio between dark matter and dark energy is a slowly varying function of the scale factor. As the dark energy component we consider two different candidates, first a quintessence scalar field, and then a tachyon field. In either case analytical solutions for the scale factor, the field, and the potential are derived. Both models show a good fit to the recent magnitude-redshift supernovae data. However, the likelihood contours disfavor the tachyon field model as it seems to prefer a excessively high value for the matter component.

  5. Measurement of the low energy spectral contribution in coincidence with valence band (VB) energy levels of Ag(100) using VB-VB coincidence spectroscopy

    NASA Astrophysics Data System (ADS)

    Gladen, R. W.; Joglekar, P. V.; Lim, Z. H.; Shastry, K.; Hulbert, S. L.; Weiss, A. H.

    A set of coincidence measurements were obtained for the study and measurement of the electron contribution arising from the inter-valence band (VB) transitions along with the inelastically scattered VB electron contribution. These Auger-unrelated contributions arise in the Auger spectrum (Ag 4p NVV) obtained using Auger Photoelectron Coincidence Spectroscopy (APECS). The measured Auger-unrelated contribution can be eliminated from Auger spectrum to obtain the spectrum related to Auger. In our VB-VB coincidence measurement, a photon beam of energy 180eV was used to probe the Ag(100) sample. The coincidence spectrum was obtained using two Cylindrical Mirror Analyzers (CMA's). The scan CMA measured the low energy electron contribution in the energy range 0-70eV in coincidence with VB electrons measured by the fixed CMA. In this talk, we present the data obtained for VB-VB coincidence at the valence band energy of 171eV along with the coincidence measurements in the energy range of 4p core and valence band. NSF DMR 0907679, NSF Award Number: 1213727. Use of the National Synchrotron Light Source, Brookhaven National Laboratory, was supported by the U.S. DOE, Office of Science, Office of Basic Energy Sciences, under Contract No. DEAC02-98CH10886.

  6. Effect of electron correlation and shape resonance on photoionization from the S1 and S2 states of pyrazine

    NASA Astrophysics Data System (ADS)

    Suzuki, Yoshi-Ichi; Suzuki, Toshinori

    2012-11-01

    In a previous study [T. Horio, T. Fuji, Y.-I. Suzuki, and T. Suzuki, J. Am. Chem. Soc. 131, 10392 (2009), 10.1021/ja904780b], we demonstrated that the time-energy map of photoelectron angular anisotropy enables unambiguous identification of ultrafast S2(ππ*)-S1(nπ*) internal conversion in pyrazine. A notable characteristic of this map is that the forbidden ionization process of D0(n-1) ← S2(ππ*) gives a negative photoelectron anisotropy parameter. In the present study, we elucidate the mechanism of this process by calculating the photoionization transition dipole moments and photoelectron angular distribution using the first-order configuration interaction method and the continuum multiple scattering Xα approximation; these calculations at the S0 equilibrium geometry reproduce the observed anisotropy parameters for D0 ← S2 and D0 ← S1 ionizations, respectively. On the other hand, they do not reproduce the small difference in the photoelectron anisotropy parameters for the D1(π-1) ← S2 and D0 ← S1 ionizations, both of which correspond to removal of an electron from the same π* orbital in the excited states. We show that these ionizations are affected by the kag shape resonance and that the difference between their photoelectron anisotropy parameters originates from the difference in the molecular geometry in D1 ← S2 and D0 ← S1.

  7. Photoionization of atoms and small molecules using synchrotron radiation. [SF/sub 6/, SiF/sub 4/

    SciTech Connect

    Ferrett, T.A.

    1986-11-01

    The combination of synchrotron radiation and time-of-flight electron spectroscopy has been used to study the photoionization dynamics of atoms (Li) and small molecules (SF/sub 6/, SiF/sub 4/, and SO/sub 2/). Partial cross sections and angular distribution asymmetry parameters have been measured for Auger electrons and photoelectrons as functions of photon energy. Emphasis is on the basic understanding of electron correlation and resonant effects as manifested in the photoemission spectra for these systems. 254 refs., 46 figs., 10 tabs.

  8. Double and triple photoionization of Li and Be

    SciTech Connect

    Colgan, J.; Pindzola, M.S.; Robicheaux, F.

    2005-08-15

    We present calculations for the double photoionization (with excitation) and the triple photoionization of Li and Be. We extend and more fully discuss the previous calculations made for Li by Colgan et al. [Phys. Rev. Lett. 93, 053201 (2004)] and present calculations for Be. The Be triple photoionization cross sections are compared with previous double shake-off model calculations of Kheifets and Bray [J. Phys. B 36, L211 (2003)], and our calculations are found to be significantly lower.

  9. Double and triple photoionization of Li and Be

    NASA Astrophysics Data System (ADS)

    Colgan, J.; Pindzola, M. S.; Robicheaux, F.

    2005-08-01

    We present calculations for the double photoionization (with excitation) and the triple photoionization of Li and Be. We extend and more fully discuss the previous calculations made for Li by Colgan et al. [Phys. Rev. Lett. 93, 053201 (2004)] and present calculations for Be. The Be triple photoionization cross sections are compared with previous double shake-off model calculations of Kheifets and Bray [J. Phys. B 36, L211 (2003)], and our calculations are found to be significantly lower.

  10. X-ray fluorescence/Auger-electron coincidence spectroscopy of vacancy cascades in atomic argon

    SciTech Connect

    Arp, U.; LeBrun, T.; Southworth, S.H.; Jung, M.; MacDonald, M.A.

    1996-12-01

    Argon L{sub 2.3}-M{sub 2.3}M{sub 2.3} Auger-electron spectra were measured in coincidence with K{alpha} fluorescent x-rays in studies of Ar K-shell vacancy decays at several photon energies above the K-threshold and on the 1s-4p resonance in atomic argon. The complex spectra recorded by conventional electron spectroscopy are greatly simplified when recorded in coincidence with fluorescent x-rays, allowing a more detailed analysis of the vacancy cascade process. The resulting coincidence spectra are compared with Hartree-Fock calculations which include shake-up transitions in the resonant case. Small energy shifts of the coincidence electron spectra are attributed to post-collision interaction with 1s photoelectrons.