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Sample records for photoelectron photoion coincidence

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

    PubMed

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

    2012-09-01

    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.

  2. 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.

  3. Synchrotron threshold photoelectron photoion coincidence spectroscopy of radicals produced in a pyrolysis source: The methyl radical

    NASA Astrophysics Data System (ADS)

    Zhu, Yupeng; Wu, Xiangkun; Tang, Xiaofeng; Wen, Zuoying; Liu, Fuyi; Zhou, Xiaoguo; Zhang, Weijun

    2016-11-01

    We present here a flash pyrolysis source coupled with a threshold photoelectron photoion coincidence (TPEPICO) spectrometer and vacuum ultraviolet synchrotron radiation to investigate the spectroscopy and photochemistry of free radicals. The radicals are produced from pyrolysis in a heated silicon carbide tube, and the TPEPICO scheme provides a strategy to obtain pure spectra of the radicals without contamination from other byproducts. As a representative example, the methyl radical was studied, and its threshold photoelectron spectrum shows a series of umbrella vibrational transitions. The adiabatic ionization energy of the methyl radical was determined to be 9.84 ± 0.01 eV.

  4. Scaling relationships in photoelectron-photoion coincidence studies: The aceton ion dissociation

    NASA Astrophysics Data System (ADS)

    Johnson, Kieth; Powis, I.; Danby, C. J.

    1981-12-01

    The distributions of internal energy released into translation in the fragmentation of energy-selected acetone ions (as determined by photoelectron-photoion coincidence studies) are shown to obey a scaling law, as do the calculated distributions derived from a statistical-dynamical phase space theory. A single function contains the dynamical history of the reaction system, at least at higher energies, in contrast to the predictions of the rigid rotor harmonic oscillator model. The scaling law provides an analysis of the bimodal form of the translational energy distributions which are found for the dissociation of the enol form of the acetone ion. This is shown to be consistent with the ergodic hypothesis.

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

    NASA Astrophysics Data System (ADS)

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

    2017-07-01

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

  6. 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.

  7. Photoelectron-photoion coincidence spectroscopy for multiplexed detection of intermediate species in a flame.

    PubMed

    Krüger, Julia; Garcia, Gustavo A; Felsmann, Daniel; Moshammer, Kai; Lackner, Alexander; Brockhinke, Andreas; Nahon, Laurent; Kohse-Höinghaus, Katharina

    2014-11-07

    Complex reactive processes in the gas phase often proceed via numerous reaction steps and intermediate species that must be identified and quantified to develop an understanding of the reaction pathways and establish suitable reaction mechanisms. Here, photoelectron-photoion coincidence (PEPICO) spectroscopy has been applied to analyse combustion intermediates present in a premixed fuel-rich (ϕ = 1.7) ethene-oxygen flame diluted with 25% argon, burning at a reduced pressure of 40 mbar. For the first time, multiplexing fixed-photon-energy PEPICO measurements were demonstrated in a chemically complex reactive system such as a flame in comparison with the scanning "threshold" TPEPICO approach used in recent pioneering combustion investigations. The technique presented here is capable of detecting and identifying multiple species by their cations' vibronic fingerprints, including radicals and pairs or triplets of isomers, from a single time-efficient measurement at a selected fixed photon energy. Vibrational structures for these species have been obtained in very good agreement with scanning-mode threshold photoelectron spectra taken under the same conditions. From such spectra, the temperature in the ionisation volume was determined. Exemplary analysis of species profiles and mole fraction ratios for isomers shows favourable agreement with results obtained by more common electron ionisation and photoionisation mass spectrometry experiments. It is expected that the multiplexing fixed-photon-energy PEPICO technique can contribute effectively to the analysis of chemical reactivity and kinetics in and beyond combustion.

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

    NASA Astrophysics Data System (ADS)

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

    2017-07-01

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

  9. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2017-06-01

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

  11. On the dissociation of the 2-pentanone ion studied by threshold photoelectron photoion coincidence spectroscopy

    NASA Astrophysics Data System (ADS)

    Kercher, James P.; Sztáray, Bálint; Baer, Tomas

    2006-03-01

    The photodissociation of 2-pentanone has been studied by threshold photoelectron photoion coincidence (TPEPICO) spectroscopy, in which ion time-of-flight (TOF) mass spectra are recorded as a function of the photon energy in the range of 9.6-12.2 eV. 2-Pentanone ions dissociate via four competitive channels: ethylene (C2H4) loss to produce the propen-2-ol ion, n-propyl (C3H7) loss to produce the acetyl ion, and two parallel methyl (CH3) loss channels, producing the butanoyl ion at low energies and the but-3-en-2-ol ion at higher energies. The latter dissociates further via ethylene (C2H4) loss providing a second pathway to the acetyl ion. This final dissociation channel is observed experimentally by the appearance of an asymmetric ion peak in the time-of-flight (TOF) distribution at photon energies greater than 11.5 eV. The ion TOF distributions and breakdown diagram have been modeled in terms of the statistical RRKM theory for unimolecular reactions, yielding the 0 K dissociation onsets of 10.239 +/- 0.015 eV for the butanoyl ion and 10.259 +/- 0.019 eV for the propen-2-ol (acetone enolate) ion. By relating the measured onsets with other well established heats of formation, the 298 K heat of formation of the butanoyl and propen-2-ol ions were determined to be 586.9 +/- 2.1 and 680.7 +/- 1.8 kJ/mol, respectively. The acetone enolate ion is thus 37 kJ/mol more stable than the acetone ion, a value supported by G3B3, and CBS-QB3 calculations. The but-3-en-2-ol ion was found to lose ethylene to produce the acetyl ion without an energy barrier.

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

    DOE PAGES

    Garcia, Gustavo A.; Tang, Xiaofeng; Gil, Jean -Francois; ...

    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

  13. 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.

  14. 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.

  15. 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.

  16. Threshold-photoelectron-spectroscopy-coincidence study of the double photoionization of HBr.

    PubMed

    Alagia, Michele; Brunetti, Brunetto G; Candori, Pietro; Falcinelli, Stefano; Teixidor, Marc Moix; Pirani, Fernando; Richter, Robert; Stranges, Stefano; Vecchiocattivi, Franco

    2004-04-15

    A threshold-photoelectron-coincidence spectrum of HBr has been recorded in the 32.2-35.8 eV photon energy range, with a resolution of approximately 0.01 eV, using a synchrotron radiation source. The X (3)Sigma(-) and a (1)Delta(2) states of the HBr(2+) dication are clearly observed in the spectrum, while there is no clear evidence for the formation of the b (1)Sigma(+) electronic state. For the first two states, the vibrational states v=0-3 have been resolved, while for the ground X (3)Sigma(-) state also spin-orbit splitting has been detected. The results appear in good agreement with previous experimental observations. A comparison with theoretical predictions indicates the role of "noncovalent" contributions to the interaction between the two atomic partners for the formation of metastable states.

  17. Ionic dissociation dynamics and energetics of hexamethyldigermanium, (CH3)6Ge2, by threshold photoelectron-photoion coincidence spectroscopy

    NASA Astrophysics Data System (ADS)

    Dávalos, Juan Z.; Baer, Tomas; Blancas, Carlos

    2017-09-01

    Threshold Photoelectron-Photoion Coincidence Spectroscopy (TPEPICO) has been used to study the ionic dissociation dynamics and energetics of Me6Ge2 (Me = CH3). Ions are energy-selected and the 0 K dissociation onsets for methyl and Me3Ge loss are obtained from the breakdown diagram and mass spectra distributions, both of them analyzed and modeled with statistical SSACM theory and quantum chemical (DFT, MP2) calculations. An updated value for the enthalpy of formation, ΔfHm0 (g) of Me6Ge2, is used to derive Δf Hm0 (Me3Ge,g) = 70.8 ± 8.9 kJ·mol-1. The bond dissociation enthalpies, BDE (Gesbnd X), of Me3Gesbnd X (X = Me, GeMe3, Cl and Br) were also derived in this study.

  18. 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.

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

    PubMed

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

    2014-01-28

    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 X(2)E of CH3Br(+) is stable, and both A(2)A1 and B(2)E 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((2)P) atom can be clearly observed in fast dissociation of CH3Br(+)(A(2)A1) ion along C-Br rupture, while a KERD of Maxwell-Boltzmann profile is obtained in dissociation of CH3Br(+)(B(2)E) ion. With the aid of the re-calculated potential energy curves of CH3Br(+) including spin-orbit coupling, dissociation mechanisms of CH3Br(+) ion in A(2)A1 and B(2)E states along C-Br rupture are revealed. For CH3Br(+)(A(2)A1) ion, the CH3 (+) + Br((2)P1/2) channel is occurred via an adiabatic dissociation by vibration, while the Br((2)P3/2) formation is through vibronic coupling to the high vibrational level of X(2)E state followed by rapid dissociation. C-Br bond breaking of CH3Br(+)(B(2)E) ion can occur via slow internal conversion to the excited vibrational level of the lower electronic states and then dissociation.

  20. Excited state dynamics in SO2. I. Bound state relaxation studied by time-resolved photoelectron-photoion coincidence spectroscopy

    NASA Astrophysics Data System (ADS)

    Wilkinson, Iain; Boguslavskiy, Andrey E.; Mikosch, Jochen; Bertrand, Julien B.; Wörner, Hans Jakob; Villeneuve, David M.; Spanner, Michael; Patchkovskii, Serguei; Stolow, Albert

    2014-05-01

    The excited state dynamics of isolated sulfur dioxide molecules have been investigated using the time-resolved photoelectron spectroscopy and time-resolved photoelectron-photoion coincidence techniques. Excited state wavepackets were prepared in the spectroscopically complex, electronically mixed ({tildeB})1B1/(Ã)1A2, Clements manifold following broadband excitation at a range of photon energies between 4.03 eV and 4.28 eV (308 nm and 290 nm, respectively). The resulting wavepacket dynamics were monitored using a multiphoton ionisation probe. The extensive literature associated with the Clements bands has been summarised and a detailed time domain description of the ultrafast relaxation pathways occurring from the optically bright ({tildeB})1B1 diabatic state is presented. Signatures of the oscillatory motion on the ({tildeB})1B1/(Ã)1A2 lower adiabatic surface responsible for the Clements band structure were observed. The recorded spectra also indicate that a component of the excited state wavepacket undergoes intersystem crossing from the Clements manifold to the underlying triplet states on a sub-picosecond time scale. Photoelectron signal growth time constants have been predominantly associated with intersystem crossing to the ({tildec})3B2 state and were measured to vary between 750 and 150 fs over the implemented pump photon energy range. Additionally, pump beam intensity studies were performed. These experiments highlighted parallel relaxation processes that occurred at the one- and two-pump-photon levels of excitation on similar time scales, obscuring the Clements band dynamics when high pump beam intensities were implemented. Hence, the Clements band dynamics may be difficult to disentangle from higher order processes when ultrashort laser pulses and less-differential probe techniques are implemented.

  1. 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.

  2. Dissociation limit and dissociation dynamic of CF4(+): application of threshold photoelectron-photoion coincidence velocity imaging.

    PubMed

    Tang, Xiaofeng; Zhou, Xiaoguo; Wu, Manman; Gao, Zhi; Liu, Shilin; Liu, Fuyi; Shan, Xiaobin; Sheng, Liusi

    2013-03-07

    Dissociation of internal energy selected CF4(+) ions in an excitation energy range of 15.40-19.60 eV has been investigated using threshold photoelectron-photoion coincidence (TPEPICO) velocity imaging. Only CF3(+) fragment ions are observed in coincident mass spectra, indicating all the X(2)T1, A(2)T2, and B(2)E ionic states of CF4(+) are fully dissociative. Both kinetic energy released distribution (KERD) and angular distribution in dissociation of CF4(+) ions have been derived from three-dimensional TPEPICO time-sliced images. A parallel distribution of CF3(+) fragments along the polarization vector of photon is observed for dissociation of CF4(+) ions in all the low-lying electronic states. With the aid of F-loss potential energy curves, dissociation mechanisms of CF4(+) ions in these electronic states have been proposed. CF4(+) ions in both X(2)T1 and A(2)T2 states directly dissociate to CF3(+) and F fragments along the repulsive C-F coordinate, while a two-step dissociation mechanism is suggested for B(2)E state: CF4(+)(B(2)E) ion first converts to the lower A(2)T2 state via internal conversion, then dissociates to CF3(+) and F fragments along the steep A(2)T2 potential energy surface. In addition, an adiabatic appearance potential of AP0(CF3(+)∕CF4) has also been established to be 14.71 ± 0.02 eV, which is very consistent with the recent calculated values.

  3. 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.

  4. 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.

  5. 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.

  6. Site-specific fragmentation caused by core-level photoionization in F(3)SiCH(2)CH(2)Si(CH(3))(3) vapor: comparison between Si:1s and 2p photoionizations by means of photoelectron-photoion-photoion triple-coincidence spectroscopy.

    PubMed

    Nagaoka, Shin-ichi; Takemoto, Mai; Prümper, Georg; Fukuzawa, Hironobu; Tamenori, Yusuke; Suzuki, Isao H; Ueda, Kiyoshi

    2008-11-28

    Site-specific fragmentation caused by Si:1s and 2p core-level photoionizations in F(3)SiCH(2)CH(2)Si(CH(3))(3) vapor was studied by energy-selected-photoelectron photoion-photoion triple-coincidence spectroscopy. The difference between the chemical shifts of the two Si sites is larger for the 1s ionization than for the 2p (2s) ionization. The fragmentation caused by the Si:1s ionization is more violent than that caused by the Si:2p ionization. The ions and ion pairs showing high site specificity for the Si:1s ionization belong to small fragments compared to those in the Si:2p ionization. Criteria for high site-specificity in fragmentation are discussed in conjunction with the present results.

  7. 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

  8. Dissociation of vibrational state-selected O2(+) Ions in the B(2)Σ(g)¯ state using threshold photoelectron-photoion coincidence velocity imaging.

    PubMed

    Tang, Xiaofeng; Zhou, Xiaoguo; Niu, Mingli; Liu, Shilin; Sheng, Liusi

    2011-06-23

    Using the recently developed threshold photoelectron-photoion coincidence (TPEPICO) velocity imaging mass spectrometer (Tang et al. Rev. Sci. Instrum.2009, 80, 113101), dissociation of vibrational state-selected O(2)(+)(B(2)Σ(g)(¯), v(+) = 0-6) ions was investigated. Both the speed and angular distributions of the O(+) fragments dissociated from individually vibronic levels of the B(2)Σ(g)(¯) state were obtained directly from the three-dimensional time-sliced TPEPICO velocity images. Two dissociation channels, O(+)((4)S) + O((3)P) and O(+)((4)S) + O((1)D), were respectively observed, and their branching ratios were found to be heavily dependent on the vibrational states. A new intersection mechanism was suggested for the predissociation of O(2)(+)(B(2)Σ(g)(¯)) ions, especially for dissociation at the energy of the v(+) = 4 level. In addition, the anisotropic parameters for O(+) fragments from different dissociative pathways were determined to be close to zero, indicating that the v(+) = 0-6 levels of B(2)Σ(g)(¯) predissociate on a time scale that is much slower than that of molecular rotation.

  9. Selected ion flow tube cation-molecule reaction studies and threshold photoelectron photoion coincidence spectroscopy of cyclic-C5F8.

    PubMed

    Parkes, Michael A; Ali, Sahangir; Tuckett, Richard P; Mikhailov, Victor A; Mayhew, Chris A

    2007-10-14

    The product ion branching ratios and rate coefficients have been measured using a selected ion flow tube (SIFT) at 298 K for the bimolecular reactions of cyclic-C5F8 with several atomic and molecular cations. The majority of reactions occur at the collisional rate calculated by the modified average dipole orientation theory, with the exception of H2O+ for which the reaction efficiency is only 55%. Apart from H2O+ and N+, the similarity of the product ion branching ratios determined from threshold photoelectron photoion coincidence (TPEPICO) and ion-molecule data suggests that long-range electron transfer is the dominant mechanism for reactions involving ions with recombination energies between 12 and 17 eV. For N+, the product ion branching ratios are very different to those produced by photoionisation; this result may be explained if some of the N-atom products are formed electronically excited. The onset of an ionisation signal of c-C5F8 measured by TPEPICO spectroscopy occurs at 12.25 +/- 0.05 eV. This is much higher than the value of the first adiabatic ionisation energy determined from electron ionisation (11.24 +/- 0.10 eV), He (I) photoionisation (11.30 +/- 0.05 eV), and an independent high resolution threshold photoelectron spectrum (11.237 +/- 0.002 eV). The ground electronic state of c-C5F8+ has very weak intensity under threshold electron conditions. The TPEPICO spectrum of c-C5F8 recorded from 12-23 eV shows detection of the parent ion and the daughter ions C4F6+ and C5F7+, with their appearance energies increasing in this order. Ion yield curves and branching ratios have been determined. Using Gaussian 03, the enthalpy of formation of c-C5F8 at 298 K has been determined to be -1495 kJ mol(-1).

  10. High-Resolution Photoelectron and Photoionization Spectroscopy

    NASA Astrophysics Data System (ADS)

    Merkt, F.

    2012-06-01

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

  11. 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.

  12. VUV state-selected photoionization of thermally-desorbed biomolecules by coupling an aerosol source to an imaging photoelectron/photoion coincidence spectrometer: case of the amino acids tryptophan and phenylalanine.

    PubMed

    Gaie-Levrel, François; Garcia, Gustavo A; Schwell, Martin; Nahon, Laurent

    2011-04-21

    Gas phase studies of biological molecules provide structural and dynamical information on isolated systems. The lack of inter- or intra-molecular interactions facilitates the interpretation of the experimental results through theoretical calculations, and constitutes an informative complement to the condensed phase. However advances in the field are partially hindered by the difficulty of vaporising these systems, most of which are thermally unstable. In this work we present a newly developed aerosol mass thermodesorption setup, which has been coupled to a Velocity Map Imaging (VMI) analyzer operated in coincidence with a Wiley-McLaren Time of Flight spectrometer, using synchrotron radiation as a single photon ionization source. Although it has been previously demonstrated that thermolabile molecules such as amino acids can be produced intact by the aerosol vaporisation technique, we show how its non-trivial coupling to a VMI analyzer plus the use of electron/ion coincidences greatly improves the concept in terms of the amount of spectroscopic and dynamic information that can be extracted. In this manner, we report on the valence shell ionization of two amino acids, tryptophan and phenylalanine, for which threshold photoelectron spectra have been recorded within the first 3 eV above the first ionization energy using synchrotron radiation emitted from the DESIRS beamline located at SOLEIL in France. Their adiabatic ionization energies (IEs) have been measured at 7.40 ± 0.05 and 8.65 ± 0.02 eV, respectively, and their spectra analyzed using existing theoretical data from the literature. The IE values agree well with previously published ones, but are given here with a considerably reduced uncertainty by up to a factor of 5. The photostability of both amino acids is also described in detail, through the measurement of the state-selected fragmentation pathways via the use of threshold electron/ion coincidences (TPEPICO), with appearance energies for the different

  13. 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.

  14. Site-Specific Electron-Relaxation Caused by Si:2p Core-Level Photoionization: Comparison between F3SiCH2CH2Si(CH3)3 and Cl3SiCH2CH2Si(CH3)3 Vapors by Means of Photoelectron Auger Electron Coincidence Spectroscopy.

    PubMed

    Nagaoka, Shin-Ichi; Kakiuchi, Takuhiro; Ohshita, Joji; Takahashi, Osamu; Hikosaka, Yasumasa

    2016-12-22

    Site-specific electron relaxations caused by Si:2p core-level photoionizations in F3SiCH2CH2Si(CH3)3 and Cl3SiCH2CH2Si(CH3)3 vapors have been studied by means of the photoelectron Auger electron coincidence spectroscopy. F3SiCH2CH2Si(CH3)3 shows almost 100% site-specificity in fragmentation caused by the Si:2p ionization. However, substitution of Cl for F of F3SiCH2CH2Si(CH3)3 considerably reduces the site-specificity at the Si atom bonded to three halogen atoms, with the site-specificity at the Si site bonded to three methyl groups remaining largely unchanged. The site-specificity reduction in Cl3SiCH2CH2Si(CH3)3 is considered to take place during the transient period between Si:L23VV Auger electron emission and the subsequent fragmentation. The reason for the reduction can be explained in terms of some differences between these two molecules in the L23VV Auger decay at the Si site bonded to the three halogen atoms.

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

    PubMed

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

    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

  16. Photoionization quantum yield for liquid squalane and squalene estimated from photoelectron emission yield

    NASA Astrophysics Data System (ADS)

    Koizumi, Hitoshi

    1994-03-01

    An equation relating photoelectron emission yield to initial photoionization quantum yield in the condensed phase is derived. The equation is applied to the photoelectron emission yields from liquid squalane (C 30H 62, 2,6,10,15,19,23-hexamethyltetracosane) and squalene (C 30H 50, 2,6,10,15,19,23-hexamethyl-2,6,10,14,18,22-tetracosahexaene) previously reported by the authors. On the assumption that the thermalization distance of photoelectrons is of a similar value to that of electrons produced with X-rays the photoionization quantum yields of these liquids in the energy region between 7 and 10.8 eV are estimated. The photoionization quantum yields are evidently less than unity and increase with increasing photon energy. The quantum yield for squalane increases monotonically whereas the one for squalene shows a change in its slope around the photoionization threshold of the σ electrons.

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

    DOE PAGES

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

    2015-10-28

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

  18. Global nonresonant vibrational-photoelectron coupling in molecular photoionization

    NASA Astrophysics Data System (ADS)

    Poliakoff, Erwin; Das, Aloke; Hardy, David; Bozek, John; Aguilar, Alex; Lucchese, Robert

    2009-05-01

    Using photoelectron spectroscopy and Schwinger variational scattering theory, we have investigated the coupling between vibrational motion and the exiting photoelectron over extended ranges of photoelectron kinetic energy. Photoelectron spectroscopy is performed with vibrational resolution over uncommonly large ranges of energy (ca. 200 eV). We find clear and significant changes in vibrational branching ratios as a function of photon energy, in direct contradiction to predictions of the Franck-Condon principle. While it is well known that resonances lead to coupling between electronic and vibrational degrees of freedom, nonresonant mechanisms that result in such coupling are not expected or well-documented. Photoelectron spectra are presented for several electronic states of N2^+, CO^+, and NO^+, and we find that valence isoelectronic channels behave very differently, which is also surprising. Theoretical results indicate that Cooper minima are the underlying cause of these effects, and we are currently working to understand the reasons for the sensitivity of the Cooper minima on bond length.

  19. 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.

  20. Time-energy mapping of photoelectron angular distribution: application to photoionization stereodynamics of nitric oxide.

    PubMed

    Suzuki, Yoshi-Ichi; Tang, Ying; Suzuki, Toshinori

    2012-05-28

    The time-energy mapping of the photoionization integral cross section and laboratory-frame photoelectron angular distribution is used to study photoionization stereodynamics of a diatomic molecule. The general theoretical formalism [Y. Suzuki and T. Suzuki, Mol. Phys., 2007, 105, 1675] is simplified for application to a diatomic molecule, and a high-resolution photoelectron imaging apparatus is used to determine the transition dipole moments and phase shifts of photoelectron partial waves in near-threshold and non-dissociative photoionization of NO from the A(2)Σ(+) state. The transition dipoles and phase shifts thus determined are in reasonable agreement with those by state-to-state photoionization experiment and Schwinger variational calculations. The difference of the phase shifts from those expected from the quantum defects of Rydberg states suggests occurrence of weak hybridization of different l-waves, in addition to the well-known s-d super complex. The circular dichroism in photoelectron angular distribution is also simulated from our results.

  1. 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

  2. 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.

  3. 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.

  4. State-to-state spectroscopy and dynamics of ions and neutrals by photoionization and photoelectron methods.

    PubMed

    Ng, Cheuk-Yiu

    2014-01-01

    Recent advances in high-resolution photoionization, photoelectron, and photodissociation studies based on single-photon vacuum ultraviolet (VUV) and two-color infrared (IR)-VUV, visible (Vis)-ultraviolet (UV), and VUV-VUV laser excitations are illustrated with selected examples. VUV laser photoionization coupled with velocity-map-imaging threshold photoelectron (VMI-TPE) detection can achieve comparable energy resolution but has higher-detection sensitivities than those observed in VUV laser pulsed field ionization photoelectron (PFI-PE) measurements. For molecules with known intermediate states, IR-VUV and Vis-UV excitation schemes are highly sensitive for rovibronically selected and resolved PFI-PE studies. The successful applications of the VUV-PFI-PE, VUV-VMI-TPE, and Vis-UV-PFI-PE methods to state-resolved and state-to-state photoelectron studies of transient radicals and transitional metal-containing molecules are highlighted. The most recently established VUV-VUV pump-probe time-slice VMI photoion method is shown to be promising for state-to-state photodissociation studies of small molecules relevant to planetary atmospheres and for the fundamental understanding of photodissociation dynamics.

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

    NASA Astrophysics Data System (ADS)

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

    2000-07-01

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

  6. High-Resolution Photoionization, Photoelectron and Photodissociation Studies. Determination of Accurate Energetic and Spectroscopic Database for Combustion Radicals and Molecules

    SciTech Connect

    Ng, Cheuk-Yiu

    2016-04-25

    The main goal of this research program was to obtain accurate thermochemical and spectroscopic data, such as ionization energies (IEs), 0 K bond dissociation energies, 0 K heats of formation, and spectroscopic constants for radicals and molecules and their ions of relevance to combustion chemistry. Two unique, generally applicable vacuum ultraviolet (VUV) laser photoion-photoelectron apparatuses have been developed in our group, which have used for high-resolution photoionization, photoelectron, and photodissociation studies for many small molecules of combustion relevance.

  7. 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.

  8. Universality of photoelectron circular dichroism in the photoionization of chiral molecules

    NASA Astrophysics Data System (ADS)

    Beaulieu, S.; Ferré, A.; Géneaux, R.; Canonge, R.; Descamps, D.; Fabre, B.; Fedorov, N.; Légaré, F.; Petit, S.; Ruchon, T.; Blanchet, V.; Mairesse, Y.; Pons, B.

    2016-10-01

    Photoionization of chiral molecules by circularly polarized radiation gives rise to a strong forward/backward asymmetry in the photoelectron angular distribution, referred to as photoelectron circular dichroism (PECD). Here we show that PECD is a universal effect that reveals the inherent chirality of the target in all ionization regimes: single photon, multiphoton, above-threshold and tunnel ionization. These different regimes provide complementary spectroscopic information at electronic and vibrational levels. The universality of the PECD can be understood in terms of a classical picture of the ionizing process, in which electron scattering on the chiral potential under the influence of a circularly polarized electric field results in a strong forward/backward asymmetry.

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

    SciTech Connect

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

    1988-09-01

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

  10. A High-resolution Vacuum Ultraviolet Laser Photoionization and Photoelectron Study of the Co Atom

    NASA Astrophysics Data System (ADS)

    Huang, Huang; Wang, Hailing; Luo, Zhihong; Shi, Xiaoyu; Chang, Yih-Chung; Ng, C. Y.

    2016-12-01

    We have measured the vacuum ultraviolet-photoionization efficiency (VUV-PIE) spectrum of Co in the energy range of 63,500-67,000 cm-1, which covers the photoionization transitions of Co(3d74s2 4F9/2) \\to Co+(3d8 3F4), Co(3d74s2 4F7/2) \\to Co+(3d8 3F3), Co(3d74s2 4F9/2) \\to Co+(3d8 3F3), Co(3d74s2 4F9/2) \\to Co+(3d8 3F2), and Co(3d74s2 4F9/2) \\to Co+(3d74s1 5F5). We have also recorded the pulsed field ionization photoelectron spectrum of Co in the same energy range, allowing accurate determinations of ionization energies (IEs) for the photoionization transitions from the Co(3d74s2 4F9/2) ground neutral state to the Co+(3F J ) (J = 4 and 3) and Co+(5F5) ionic states, as well as from the Co(3d74s2 4F7/2) excited neural state to the Co+(3d8 3F3) ionic state. The high-resolution nature of the VUV laser used has allowed the observation of many well-resolved autoionizing resonances in the VUV-PIE spectrum, among which an autoionizing Rydberg series, 3d74s1(5F5)np (n = 19-38), converging to the Co+(3d74s1 5F5) ionic state from the Co(3d74s2 4F9/2) ground neutral state is identified. The fact that no discernible step-like structures are present at these ionization thresholds in the VUV-PIE spectrum indicates that direct photoionization of Co is minor compared to autoionization in this energy range. The IE values, the autoionizing Rydberg series, and the photoionization cross sections obtained in this experiment are valuable for understanding the VUV opacity and abundance measurement of the Co atom in stars and solar atmospheres, as well as for benchmarking the theoretical results calculated in the Opacity Project and the IRON Project, and thus are of relevance to astrophysics.

  11. Rovibronically selected and resolved two-color laser photoionization and photoelectron study of nickel carbide cation.

    PubMed

    Chang, Yih Chung; Shi, Xiaoyu; Lau, Kai-Chung; Yin, Qing-Zhu; Liou, H T; Ng, C Y

    2010-08-07

    We have performed a two-color laser photoionization and photoelectron study of nickel carbide (NiC) and its cation (NiC(+)). By preparing NiC in a single rovibronic level of an intermediate vibronic state via visible laser excitation prior to ultraviolet laser photoionization, we have measured the photoionization efficiency spectrum of NiC near its ionization threshold, covering the formation of NiC(+)(X (2)Sigma(+);v(+)=0-3). We have also obtained well-resolved rotational transitions for the v(+)=0 and 1 vibrational bands of the NiC(+)(X (2)Sigma(+)) ground state. The assignment of rotational transitions observed between the neutral NiC intermediate state and the NiC(+) ion ground state has allowed the direct determination of a highly precise value for the ionization energy of NiC, IE(NiC)=67,525.1+/-0.5 cm(-1) (8.372 05+/-0.000 06 eV). This experiment also provides reliable values for the vibrational spacing [DeltaG(1/2)=859.5+/-0.5 cm(-1)], rotational constants (B(e)(+)=0.6395+/-0.0018 cm(-1) and alpha(e)(+)=0.0097+/-0.0009 cm(-1)), and equilibrium bond distance (r(e)(+)=1.628 A) for the NiC(+)(X (2)Sigma(+)) ground state. The experimental results presented here are valuable for benchmarking the development of more reliable ab initio quantum computation procedures for energetic and spectroscopic calculations of transition metal-containing molecules.

  12. Rovibronically selected and resolved two-color laser photoionization and photoelectron study of nickel carbide cation

    NASA Astrophysics Data System (ADS)

    Chang, Yih Chung; Shi, Xiaoyu; Lau, Kai-Chung; Yin, Qing-Zhu; Liou, H. T.; Ng, C. Y.

    2010-08-01

    We have performed a two-color laser photoionization and photoelectron study of nickel carbide (NiC) and its cation (NiC+). By preparing NiC in a single rovibronic level of an intermediate vibronic state via visible laser excitation prior to ultraviolet laser photoionization, we have measured the photoionization efficiency spectrum of NiC near its ionization threshold, covering the formation of NiC+(X Σ2+;v+=0-3). We have also obtained well-resolved rotational transitions for the v+=0 and 1 vibrational bands of the NiC+(X Σ2+) ground state. The assignment of rotational transitions observed between the neutral NiC intermediate state and the NiC+ ion ground state has allowed the direct determination of a highly precise value for the ionization energy of NiC, IE(NiC)=67 525.1±0.5 cm-1 (8.372 05±0.000 06 eV). This experiment also provides reliable values for the vibrational spacing [ΔG(1/2)=859.5±0.5 cm-1], rotational constants (Be+=0.6395±0.0018 cm-1 and αe+=0.0097±0.0009 cm-1), and equilibrium bond distance (re+=1.628 Å) for the NiC+(X Σ2+) ground state. The experimental results presented here are valuable for benchmarking the development of more reliable ab initio quantum computation procedures for energetic and spectroscopic calculations of transition metal-containing molecules.

  13. Near-threshold photoelectron angular distributions from two-photon resonant photoionization of He

    NASA Astrophysics Data System (ADS)

    O'Keeffe, P.; Mihelič, A.; Bolognesi, P.; Žitnik, M.; Moise, A.; Richter, R.; Avaldi, L.

    2013-01-01

    Two-photon resonant photoionization of helium is investigated both experimentally and theoretically. Ground state helium atoms are excited to the 1s4p, 1s5p and 1s6p 1P states by synchrotron radiation and ionized by a synchronized infrared pulsed picosecond laser. The photoelectron angular distributions of the emitted electrons are measured using a velocity map imaging (VMI) spectrometer. The measured asymmetry parameters of the angular distribution allow the phase differences and the ratios of the dipole matrix elements of the 1sɛs and 1sɛd channels to be determined. The experimental results agree with the calculated values obtained in a configuration-interaction calculation with a Coulomb-Sturmian basis set. The effects of the radiative decay of the intermediate state and the static electric field of the VMI spectrometer on the measurements are discussed.

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

    PubMed

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

    2008-09-28

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

  15. Photoelectron and photoion spectroscopy of atoms, nanoparticles, and nanoplasmas irradiated with strong femtosecond laser fields

    NASA Astrophysics Data System (ADS)

    Hickstein, Daniel D.

    Modern femtosecond lasers can produce pulses of light that are shorter than the vibrational periods in molecules and have electric fields stronger than the Coulomb field that binds electrons in atoms. These short pulse lasers enable the observation of chemical reactions, the production of attosecond bursts of high-energy photons, and the precision-machining of solid materials with minimal heat transport to the material. In this thesis, I describe three experiments that provide new insight into strong-field (1014 Watts/cm2) femtosecond laser-matter interactions in three important regimes. First, I discuss the strong-field ionization of gas-phase atoms, identify a new structure in the photoelectron angular distribution of xenon gas, and explain this structure as a result of field-driven electrons colliding with the Coulomb potential of the ion. Second, I describe a new method to perform photoelectron and photoion spectroscopy on single, isolated nanoparticles and demonstrate this technique by observing the directional ion ejection that takes place in the laser ablation of nanostructures. Finally, I present the first experimental observations of shock wave propagation in nanoscale plasmas. These findings will guide future efforts to probe the structure of atoms and molecules on the femtosecond timescale, design nanomaterials that enhance light on the subwavelength scale, and produce high-energy ions from plasmas.

  16. 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.

  17. Rovibronically selected and resolved two-color laser photoionization and photoelectron study of cobalt carbide cation.

    PubMed

    Huang, Huang; Chang, Yih Chung; Luo, Zhihong; Shi, Xiaoyu; Lam, Chow-Shing; Lau, Kai-Chung; Ng, C Y

    2013-03-07

    We have conducted a two-color visible-ultraviolet (VIS-UV) resonance-enhanced laser photoionization efficiency and pulsed field ionization-photoelectron (PFI-PE) study of gaseous cobalt carbide (CoC) near its ionization onset in the total energy range of 61,200-64,510 cm(-1). The cold gaseous CoC sample was prepared by a laser ablation supersonically cooled beam source. By exciting CoC molecules thus generated to single N' rotational levels of the intermediate CoC∗((2)Σ(+); v') state using a VIS dye laser prior to UV laser photoionization, we have obtained N(+) rotationally resolved PFI-PE spectra for the CoC(+)(X(1)Σ(+); v(+) = 0 and 1) ion vibrational bands free from interference by impurity species except Co atoms produced in the ablation source. The rotationally selected and resolved PFI-PE spectra have made possible unambiguous rotational assignments, yielding accurate values for the adiabatic ionization energy of CoC(X(2)Σ(+)), IE(CoC) = 62,384.3 ± 0.6 cm(-1) (7.73467 ± 0.00007 eV), the vibrational frequency ωe (+) = 985.6 ± 0.6 cm(-1), the anharmonicity constant ωe (+)χe (+) = 6.3 ± 0.6 cm(-1), the rotational constants (Be (+) = 0.7196 ± 0.0005 cm(-1), αe (+) = 0.0056 ± 0.0008 cm(-1)), and the equilibrium bond length re (+) = 1.534 Å for CoC(+)(X(1)Σ(+)). The observation of the N(+) = 0 level in the PFI-PE measurement indicates that the CoC(+) ground state is of (1)Σ(+) symmetry. Large ΔN(+) = N(+) - N' changes up to 6 are observed for the photoionization transitions CoC(+)(X(1)Σ(+); v(+) = 0-2; N(+)) ← CoC∗((2)Σ(+); v'; N' = 6, 7, 8, and 9). The highly precise energetic and spectroscopic data obtained in the present study have served as a benchmark for testing theoretical predictions based on state-of-the-art ab initio quantum calculations at the CCSDTQ∕CBS level of theory as presented in the companion article.

  18. Quasibound continuum states in SiF4 (D~ 2A1) photoionization: Photoelectron-vibrational coupling

    NASA Astrophysics Data System (ADS)

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

    2007-06-01

    The authors report a fully vibrationally resolved photoelectron spectroscopy investigation of a nonplanar molecule studied over a range of excitation energies. Experimental results for all four fundamental vibrational modes are presented. In each case significant non-Franck-Condon effects are seen. The vibrational branching ratio for the totally symmetric mode ν1+ is found to be strongly affected by resonant excitation in the SiF4+ (D˜A12) photoionization channel. This is shown to be the result of two distinct shape resonances, which for the first time have been both confirmed by theoretical calculations. Vibrationally resolved Schwinger photoionization calculations are used to understand the vibronic coupling for the photoelectrons, both using ab initio and harmonic vibrational wave functions.

  19. 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.

  20. 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.

  1. Insight on hole-hole interaction and magnetic order from dichroic auger-photoelectron coincidence spectra.

    PubMed

    Cini, M; Perfetto, E; Gotter, R; Offi, F; Ruocco, A; Stefani, G

    2011-11-18

    The absence of sharp structures in the Auger line shapes of partially filled bands has severely limited the use of electron spectroscopy in magnetic crystals and other correlated materials. By a novel interplay of experimental and theoretical techniques we achieve a combined understanding of the photoelectron, Auger, and Auger-photoelectron coincidence spectra (APECS) of the antiferromagnetic CoO. A recently discovered dichroic effect in angle resolved (DEAR) APECS reveals a complex pattern in the Auger line shape, which is here explained in detail, labeling the final states by their total spin. Since the dichroic effect exists in the antiferromagnetic state but vanishes at the Néel temperature, the DEAR-APECS technique detects the phase transition from its local effects, thus providing a unique tool to observe and understand magnetic correlations where the usual methods are not applicable.

  2. The LVV Auger line shape of sulfur on copper studied by Auger photoelectron coincidence spectroscopy.

    PubMed

    Di Filippo, G; Trioni, M I; Fratesi, G; Schumann, F O; Wei, Z; Li, C H; Behnke, L; Patil, S; Kirschner, J; Stefani, G

    2015-03-04

    We have studied the line shapes of Cu(0 0 1)-p (2 × 2)S L2VV and L3VV Auger decay by means of Auger photoelectron coincidence spectroscopy. Measuring the LVV Auger spectrum in coincidence with S 2p1/2 and 2p3/2 photoelectrons respectively, we have been able to separate the two overlapping Auger spectra and determine their intrinsic line shapes. The two Auger transitions, though shifted in energy, display an identical line shape whose main features can be qualitatively understood considering a single particle approximation but are better described within a Cini-Sawatzky (CS) approach. Comparison between the experimental and the CS calculated spectra confirms that a substantial part of the Auger lines (∼20%) can be ascribed to decay events accompanied by the excitation of one additional electron-hole pair in the valence band. For the first time, the locality of the Auger process combined with the surface sensitivity of the APECS technique and its ability to separate overlapping structures are used to study Auger transitions taking place at the the surface states of a S/noble-metal interface.

  3. 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})

  4. 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.

  5. Theoretical description of circular dichroism in photoelectron angular distributions of randomly oriented chiral molecules after multi-photon photoionization

    NASA Astrophysics Data System (ADS)

    Goetz, R. E.; Isaev, T. A.; Nikoobakht, B.; Berger, R.; Koch, C. P.

    2017-01-01

    Photoelectron circular dichroism refers to the forward/backward asymmetry in the photoelectron angular distribution with respect to the propagation axis of circularly polarized light. It has recently been demonstrated in femtosecond multi-photon photoionization experiments with randomly oriented camphor and fenchone molecules [C. Lux et al., Angew. Chem., Int. Ed. 51, 4755 (2012) and C. S. Lehmann et al., J. Chem. Phys. 139, 234307 (2013)]. A theoretical framework describing this process as (2+1) resonantly enhanced multi-photon ionization is constructed, which consists of two-photon photoselection from randomly oriented molecules and successive one-photon ionization of the photoselected molecules. It combines perturbation theory for the light-matter interaction with ab initio calculations for the two-photon absorption and a single-center expansion of the photoelectron wavefunction in terms of hydrogenic continuum functions. It is verified that the model correctly reproduces the basic symmetry behavior expected under exchange of handedness and light helicity. When applied to fenchone and camphor, semi-quantitative agreement with the experimental data is found, for which a sufficient d wave character of the electronically excited intermediate state is crucial.

  6. 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.

  7. 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.

  8. Electronic Properties of Gallium Arsenide Surfaces as Characterized by Inverse Photoemission and Auger Photoelectron Coincidence Spectroscopy.

    NASA Astrophysics Data System (ADS)

    Garrison, Karl Claudius

    The unoccupied electronic band structure of GaAs(100) has been probed using k-resolved inverse photoemission spectroscopy (KRIPES). The use of As-capped MBE-grown GaAs(100) surface has enabled us to obtain well-ordered surfaces that exhibit reconstructions characteristic of both the As-terminated (2 x 4) and the Ga-terminated (4 x 2) GaAs(100) surfaces. By studying the electronic structure of two different surface reconstructions on the same bulk semiconductor, we have been able to correlate the electronic structure of GaAs(100) with its geometric structure. In particular, we have detected a surface state at ~1.6 eV above the Fermi level that disperses with the incident electron angle. This state has been associated with the empty Ga-dangling bond and is only seen on the Ga-terminated (4 x 2) surface of GaAs(100). The energy of this state, however, is significantly higher than predicted by total energy DOS calculations. This discrepancy has been associated with quasiparticle excitations not included in the calculations. Using Auger photoelectron coincidence spectroscopy (APECS), we have also studied the core-valence-valance (CVV) Auger decay process for the GaAs(110) surface. APECS enables us to independently separate the Ga-derived and As-derived Auger spectra and to clearly resolve the s-s and s-p Auger contributions. This has led to the discovery of surface-specific electron correlation effects, which have been directly observed for the first time in this study. In addition, we have also investigated the growth of a new class of metallic overlayers on III-V semiconductors: thermally stable, epitaxial, single crystal metallic compound growth on MBE-grown GaAs(100). In particular, we have grown CoGa and ErAs metallic thin films on GaAs(100) and have investigated their properties using a variety of techniques to study the quality of the thin films both during and after growth. Our studies have shown both compounds form good quality single crystals when grown on an

  9. Site-specific recoil-induced effects on inner-shell photoionization of linear triatomic molecules: N 1 s photoelectron spectra of N2 O

    NASA Astrophysics Data System (ADS)

    Krivosenko, Yu. S.; Pavlychev, A. A.

    2016-11-01

    We investigate hard X-ray ionization of linear triatomic molecules accenting recoil-induced effects on the dynamics of molecular frame. This dynamics is studied within the two-springs and harmonic approximations. The mode-channel relationship connecting the excitations of vibrational, rotational and translational degrees of freedom with the Σ → Σ and Σ → Π photoionization channels is applied to compute the N 1s-1 photoelectron spectra of molecular N2 O for various photon energies. The distinct ionized-site- and molecular-orientation-specific changes in the vibration structure of the 1 s photoelectron lines of terminal and central nitrogen atoms are revealed and discussed.

  10. Wavelength dependent photoelectron circular dichroism of limonene studied by femtosecond multiphoton laser ionization and electron-ion coincidence imaging

    NASA Astrophysics Data System (ADS)

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

    2016-09-01

    Enantiomers of the monoterpene limonene have been investigated by (2 + 1) resonance enhanced multiphoton ionization and photoelectron circular dichroism employing tuneable, circularly polarized femtosecond laser pulses. Electron imaging detection provides 3D momentum measurement while electron-ion coincidence detection can be used to mass-tag individual electrons. Additional filtering, by accepting only parent ion tagged electrons, can be then used to provide discrimination against higher energy dissociative ionization mechanisms where more than three photons are absorbed to better delineate the two photon resonant, one photon ionization pathway. The promotion of different vibrational levels and, tentatively, different electronic ion core configurations in the intermediate Rydberg states can be achieved with different laser excitation wavelengths (420 nm, 412 nm, and 392 nm), in turn producing different state distributions in the resulting cations. Strong chiral asymmetries in the lab frame photoelectron angular distributions are quantified, and a comparison made with a single photon (synchrotron radiation) measurement at an equivalent photon energy.

  11. 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.

  12. Internal energy dependence of the photodissociation dynamics of O3(-) using cryogenic photoelectron-photofragment coincidence spectroscopy.

    PubMed

    Shen, Ben B; Benitez, Yanice; Lunny, Katharine G; Continetti, Robert E

    2017-09-07

    Photoelectron-photofragment coincidence (PPC) spectra of ozonide, O3(-), were measured at 388 nm (Ehν = 3.20 eV) using a newly constructed cryogenic octopole accumulation trap coupled to a PPC spectrometer. The photoelectron spectra reveal three processes consisting of a stable photodetachment channel, and two distinct photodissociation pathways yielding (1) O2 + O(-) or (2) O + O2(-). The first photodissociation pathway is observed in the PPC spectra by photodetachment of the O(-) product by a second photon, and produces electronically excited O2((1)Δg). The O2(-) product of the second photodissociation pathway undergoes autodetachment for O2(-)((2)Πg, v″ > 4), a process greatly enhanced by vibrational excitation of the precursor O3(-). Cooling anions thermalized at 300 K to <17 K in a cryogenic octopole accumulation trap essentially turns off this autodetachment pathway. The product kinetic energy distribution in coincidence with the autodetached electrons from O2(-)(v″ = 4) exhibits resolved features consistent with bend (ν2), asymmetric stretch (ν3) and a stretching combination band (ν1 + ν3) in the intermediate electronic state, illustrating the insights that can be gained from kinematically complete measurements. These results are discussed in the context of the low-lying excited states of O3(-).

  13. 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.

  14. 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.

  15. 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.

  16. 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.

  17. 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.

  18. Tracking hole localization in K -shell and core-valence-excited acetylene photoionization via body-frame photoelectron angular distributions

    NASA Astrophysics Data System (ADS)

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

    2015-02-01

    Asymmetry in the molecular-frame photoelectron angular distributions from core-hole- or core-valence-excited polyatomic targets with symmetry-equivalent atoms can provide direct evidence for core-hole localization. Using acetylene as an example, we contrast the small asymmetry that can be seen in direct core-level ionization, due to the competition between two competing pathways to the continuum, with ionization from core-valence-excited HCCH, which offers the prospect of observing markedly greater asymmetry.

  19. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2014-10-01

    Titanium carbide and its cation (TiC/TiC+) 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-1. Based on rotational analyses, these bands are assigned as the respective TiC(3Π1) ← TiC(X3Σ+) and TiC(3Σ+) ← TiC(X3Σ+) transition bands. This assignment supports that the electronic configuration and term symmetry for the neutral TiC ground state are …7σ28σ19σ13π4 (X3Σ+). The rotational constant and the corresponding bond distance of TiC(X3Σ+; v″ = 0) are determined to be B0″ = 0.6112(10) cm-1 and r0″ = 1.695(2) Å, respectively. The rotational analyses of the VIS-UV-PFI-PE spectra for the TiC+(X; v+ = 0 and 1) vibrational bands show that the electronic configuration and term symmetry for the ionic TiC+ ground state are …7σ28σ13π4 (X2Σ+) with the v+ = 0 → 1 vibrational spacing of 870.0(8) cm-1 and the rotational constants of Be+ = 0.6322(28) cm-1, and αe+ = 0.0085(28) cm-1. The latter rotational constants yield the equilibrium bond distance of re+ = 1.667(4) Å for TiC+(X2Σ+). The cleanly rotationally resolved VIS-UV-PFI-PE spectra have also provided a highly precise value of 53 200.2(8) cm-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 (D0) of TiC+(X2Σ+) and that of TiC(X3Σ+) to be D0(Ti+-C) - D0(Ti-C) = 0.2322(2) eV. Similar to previous experimental observations, the present state-to-state PFI-PE study of the photoionization transitions, TiC+(X2Σ+; v+ = 0 and 1, N+) ← TiC(3Π1; v', J'), reveals a strong decreasing trend for the photoionization cross section as |ΔN+| = |N+ - J'| is increased. The maximum |ΔN+| change of 7 observed here is also consistent with the previous

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

    PubMed

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

    2014-10-14

    Titanium carbide and its cation (TiC/TiC(+)) 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(-1). Based on rotational analyses, these bands are assigned as the respective TiC((3)Π1) ← TiC(X(3)Σ(+)) and TiC((3)Σ(+)) ← TiC(X(3)Σ(+)) transition bands. This assignment supports that the electronic configuration and term symmetry for the neutral TiC ground state are …7σ(2)8σ(1)9σ(1)3π(4) (X(3)Σ(+)). The rotational constant and the corresponding bond distance of TiC(X(3)Σ(+); v″ = 0) are determined to be B0″ = 0.6112(10) cm(-1) and r0″ = 1.695(2) Å, respectively. The rotational analyses of the VIS-UV-PFI-PE spectra for the TiC(+)(X; v(+) = 0 and 1) vibrational bands show that the electronic configuration and term symmetry for the ionic TiC(+) ground state are …7σ(2)8σ(1)3π(4) (X(2)Σ(+)) with the v(+) = 0 → 1 vibrational spacing of 870.0(8) cm(-1) and the rotational constants of B(e)(+) = 0.6322(28) cm(-1), and α(e)(+) = 0.0085(28) cm(-1). The latter rotational constants yield the equilibrium bond distance of r(e)(+) = 1.667(4) Å for TiC(+)(X(2)Σ(+)). The cleanly rotationally resolved VIS-UV-PFI-PE spectra have also provided a highly precise value of 53 200.2(8) cm(-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 (D0) of TiC(+)(X(2)Σ(+)) and that of TiC(X(3)Σ(+)) to be D0(Ti(+)-C) - D0(Ti-C) = 0.2322(2) eV. Similar to previous experimental observations, the present state-to-state PFI-PE study of the photoionization transitions, TiC(+)(X(2)Σ(+); v(+) = 0 and 1, N(+)) ← TiC((3)Π1; v', J'), reveals a strong decreasing trend for the photoionization cross section as |ΔN(+)| = |N

  2. Photoionization studies of oxygen and hydrogen

    NASA Astrophysics Data System (ADS)

    Padmanabhan, Arathi

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

  3. 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

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

    NASA Astrophysics Data System (ADS)

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

    2012-11-01

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

  5. Investigation of the reaction of hydroxy and carbon monoxide to form hydrogen and carbon dioxide by Photoelectron-Photofragment Coincidence spectroscopy in a cryogenic ion beam trap

    NASA Astrophysics Data System (ADS)

    Johnson, Christopher Joseph

    2011-12-01

    The HOCO radical plays a crucial role in a wide variety of chemical processes, including atmospheric CO2 regulation and combustion chemistry, as an intermediate in the elementary reaction OH + CO → H + CO2 . However, scant information exists on this species due to the difficulties in studying it. Previous photoelectron-photofragment coincidence (PPC) studies performed in this laboratory have identified key processes occurring on the HOCO potential energy surface, but are complicated by the presence of internal excitation in the precursor anions, leading to uncertainties in product energies and dynamics. To address this, a new instrument has been constructed which incorporates a cryogenically cooled linear electrostatic storage device, providing a cold source of anions for dissociative photodetachment studies by PPC spectroscopy. The enhanced resolution and well-characterized energetics provided by this instrument have allowed the fundamental energetics and processes occurring on the HOCO potential energy surface to be studied in unprecedented detail. New data shows unambiguous confirmation of the presence of tunneling in the reaction HOCO → H + CO2. Careful study of this product channel has led to the generation a model one-dimensional potential barrier describing this process directly from experimental tunneling data, and tunneling lifetimes over a range of relevant internal energies to be predicted. High resolution photodetachment experiments provide a reassignment of the electron affinities of both cis- and trans-HOCO and the determination of several normal mode frequencies not previously measured in the gas phase, each with the support of high-level ab initio quantum chemical calculations. Further details on the previously-unknown isomer well depths and the process of isomerization have been extracted using this information. Finally, nonresonant two-photon photodetachment studies of NO2 -, a species with striking electronic structure similarities to HOCO

  6. Tabletop Femtosecond VUV Photoionization and PEPICO Detection of Microreactor Pyrolysis Products

    DOE PAGES

    Couch, David E.; Buckingham, Grant T.; Baraban, Joshua H.; ...

    2017-06-29

    Here, we report the combination of tabletop vacuum ultraviolet photoionization with photoion--photoelectron coincidence spectroscopy for sensitive, isomer-specific detection of nascent products from a pyrolysis microreactor. Results on several molecules demonstrate two essential capabilities that are very straightforward to implement: the ability to differentiate isomers, and to distinguish thermal products from dissociative ionization. We derive vacuum ultraviolet light is from a commercial tabletop femtosecond laser system, allowing data to be collected at 10 kHz; this high repetition rate is critical for coincidence techniques. The photoion—photoelectron coincidence spectrometer uses the momentum of the ion to identify dissociative ionization events, and coincidence techniquesmore » to provide a photoelectron spectrum specific to each mass, which is used to distinguish different isomers. We also have used this spectrometer to detect the pyrolysis products that result from the thermal cracking of acetaldehyde, cyclohexene, and 2-butanol. The photoion—photoelectron spectrometer can detect and identify organic radicals and reactive intermediates that result from pyrolysis. Direct comparison of laboratory and synchrotron data illustrate the advantages and potential of this approach.« less

  7. Surface-site-selective study of valence electronic states of a clean Si(111)-7x7 surface using Si L{sub 23}VV Auger electron and Si 2p photoelectron coincidence measurements

    SciTech Connect

    Kakiuchi, Takuhiro; Tahara, Masashi; Nagaoka, Shin-ichi; Hashimoto, Shogo; Fujita, Narihiko; Tanaka, Masatoshi; Mase, Kazuhiko

    2011-01-15

    Valence electronic states of a clean Si(111)-7x7 surface are investigated in a surface-site-selective way using high-resolution coincidence measurements of Si pVV Auger electrons and Si 2p photoelectrons. The Si L{sub 23}VV Auger electron spectra measured in coincidence with energy-selected Si 2p photoelectrons show that the valence band at the highest density of states in the vicinity of the rest atoms is shifted by {approx}0.95 eV toward the Fermi level (E{sub F}) relative to that in the vicinity of the pedestal atoms (atoms directly bonded to the adatoms). The valence-band maximum in the vicinity of the rest atoms, on the other hand, is shown to be shifted by {approx}0.53 eV toward E{sub F} relative to that in the vicinity of the pedestal atoms. The Si 2p photoelectron spectra of Si(111)-7x7 measured in coincidence with energy-selected Si L{sub 23}VV Auger electrons identify the topmost surface components, and suggest that the dimers and the rest atoms are negatively charged while the pedestal atoms are positively charged. Furthermore, the Si 2p-Si L{sub 23}VV photoelectron Auger coincidence spectroscopy directly verifies that the adatom Si 2p component (usually denoted by C{sub 3}) is correlated with the surface state just below E{sub F} (usually denoted by S{sub 1}), as has been observed in previous angle-resolved photoelectron spectroscopy studies.

  8. Ultrafast Dynamics in Postcollision Interaction after Multiple Auger Decays in Argon 1s Photoionization

    NASA Astrophysics Data System (ADS)

    Guillemin, R.; Sheinerman, S.; Bomme, C.; Journel, L.; Marin, T.; Marchenko, T.; Kushawaha, R. K.; Trcera, N.; Piancastelli, M. N.; Simon, M.

    2012-07-01

    Argon 1s photoionization followed by multiple Auger decays is investigated both experimentally, by means of photoelectron-ion coincidences, and theoretically. A strong influence of the different Auger decays on the photoelectron spectra is observed through postcollision interaction which shifts the maximum of the energy distribution and distorts the spectral shape. A good agreement between the calculated and measured spectra for selected Arn+ ions (n=1-5) allows one to estimate the widths (lifetimes) of the intermediate states for each specific decay pathway.

  9. 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.

  10. 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.

  11. Breaking through the false coincidence barrier in electron–ion coincidence experiments

    DOE PAGES

    Osborn, David L.; Hayden, Carl C.; Hemberger, Patrick; ...

    2016-10-31

    Photoelectron Photoion Coincidence (PEPICO) spectroscopy holds the promise of a universal, isomer-selective, and sensitive analytical technique for time-resolved quantitative analysis of bimolecular chemical reactions. Unfortunately, its low dynamic range of ~103 has largely precluded its use for this purpose, where a dynamic range of at least 105 is generally required. This limitation is due to the false coincidence background common to all coincidence experiments, especially at high count rates. Electron/ion pairs emanating from separate ionization events but arriving within the ion time of flight (TOF) range of interest constitute the false coincidence background. Although this background has uniform intensity atmore » every m/z value, the Poisson scatter in the false coincidence background obscures small signals. In this paper, temporal ion deflection coupled with a position-sensitive ion detector enables suppression of the false coincidence background, increasing the dynamic range in the PEPICO TOF mass spectrum by 2–3 orders of magnitude. The ions experience a time-dependent electric deflection field at a well-defined fraction of their time of flight. This deflection defines an m/z- and ionization-time dependent ion impact position for true coincidences, whereas false coincidences appear randomly outside this region and can be efficiently suppressed. When cold argon clusters are ionized, false coincidence suppression allows us to observe species up to Ar9+, whereas Ar4+ is the largest observable cluster under traditional operation. As a result, this advance provides mass-selected photoelectron spectra for fast, high sensitivity quantitative analysis of reacting systems.« less

  12. Breaking through the false coincidence barrier in electron–ion coincidence experiments

    SciTech Connect

    Osborn, David L.; Hayden, Carl C.; Hemberger, Patrick; Bodi, Andras; Voronova, Krisztina; Sztaray, Balint

    2016-10-31

    Photoelectron Photoion Coincidence (PEPICO) spectroscopy holds the promise of a universal, isomer-selective, and sensitive analytical technique for time-resolved quantitative analysis of bimolecular chemical reactions. Unfortunately, its low dynamic range of ~103 has largely precluded its use for this purpose, where a dynamic range of at least 105 is generally required. This limitation is due to the false coincidence background common to all coincidence experiments, especially at high count rates. Electron/ion pairs emanating from separate ionization events but arriving within the ion time of flight (TOF) range of interest constitute the false coincidence background. Although this background has uniform intensity at every m/z value, the Poisson scatter in the false coincidence background obscures small signals. In this paper, temporal ion deflection coupled with a position-sensitive ion detector enables suppression of the false coincidence background, increasing the dynamic range in the PEPICO TOF mass spectrum by 2–3 orders of magnitude. The ions experience a time-dependent electric deflection field at a well-defined fraction of their time of flight. This deflection defines an m/z- and ionization-time dependent ion impact position for true coincidences, whereas false coincidences appear randomly outside this region and can be efficiently suppressed. When cold argon clusters are ionized, false coincidence suppression allows us to observe species up to Ar9+, whereas Ar4+ is the largest observable cluster under traditional operation. As a result, this advance provides mass-selected photoelectron spectra for fast, high sensitivity quantitative analysis of reacting systems.

  13. Breaking through the false coincidence barrier in electron-ion coincidence experiments

    NASA Astrophysics Data System (ADS)

    Osborn, David L.; Hayden, Carl C.; Hemberger, Patrick; Bodi, Andras; Voronova, Krisztina; Sztáray, Bálint

    2016-10-01

    Photoelectron Photoion Coincidence (PEPICO) spectroscopy holds the promise of a universal, isomer-selective, and sensitive analytical technique for time-resolved quantitative analysis of bimolecular chemical reactions. Unfortunately, its low dynamic range of ˜103 has largely precluded its use for this purpose, where a dynamic range of at least 105 is generally required. This limitation is due to the false coincidence background common to all coincidence experiments, especially at high count rates. Electron/ion pairs emanating from separate ionization events but arriving within the ion time of flight (TOF) range of interest constitute the false coincidence background. Although this background has uniform intensity at every m/z value, the Poisson scatter in the false coincidence background obscures small signals. In this paper, temporal ion deflection coupled with a position-sensitive ion detector enables suppression of the false coincidence background, increasing the dynamic range in the PEPICO TOF mass spectrum by 2-3 orders of magnitude. The ions experience a time-dependent electric deflection field at a well-defined fraction of their time of flight. This deflection defines an m/z- and ionization-time dependent ion impact position for true coincidences, whereas false coincidences appear randomly outside this region and can be efficiently suppressed. When cold argon clusters are ionized, false coincidence suppression allows us to observe species up to Ar9+, whereas Ar4+ is the largest observable cluster under traditional operation. This advance provides mass-selected photoelectron spectra for fast, high sensitivity quantitative analysis of reacting systems.

  14. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2013-03-01

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

  16. Rotational distributions of molecular photoions following resonant excitation

    NASA Astrophysics Data System (ADS)

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

    1986-11-01

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

  17. Photoionization Dynamics of Small Molecules

    SciTech Connect

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

    1985-01-01

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

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

    PubMed

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

    2012-01-12

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

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

    NASA Astrophysics Data System (ADS)

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

    2017-03-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2015-09-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2011-02-01

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

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

    PubMed

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

    2011-02-14

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

  3. 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. 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.

  5. Direct Observations of Correlation between Si-2p Components and Surface States on Si(110)-16 × 2 Single-Domain Surface Using Si-L23VV Auger-Electron and Si-2p Photoelectron Coincidence Measurements

    NASA Astrophysics Data System (ADS)

    Kakiuchi, Takuhiro; Yoshizaki, Yuya; Kubota, Hiroyuki; Sato, Yuki; Nagaoka, Shin-ichi; Mase, Kazuhiko

    2017-05-01

    A Si(110)-16 × 2 single-domain (SD) surface is investigated in a site-selective way using Si L23VV Auger-electron Si-2p photoelectron coincidence spectroscopy (Si-L23VV-Si-2p APECS) and Si-2p photoelectron Si-L23VV Auger-electron coincidence spectroscopy (Si-2p-Si-L23VV PEACS). The Si(110)-16 × 2 SD consists of five Si-2p surface components (SC1-SC5) and has four semiconducting surface states (S1-S4). The Si-L2VV-Si-2p1/2 APECS spectrum of the Si(110)-16 × 2 SD measured in coincidence with Si-2p1/2 photoelectrons of SC3, SC4, and SC5 shows two small shoulders in the higher Auger electron kinetic energy (AeKE) region. These shoulders suggest Auger processes involving the surface states S1 and S3. The spectral weights of SC3, SC4, and SC5 Si-2p components are greatly enhanced in the Si-2p-Si-L23VV PEACS spectrum measured at Auger electrons with an AeKE of +5.0 eV relative to the Si L23VV peak. On the other hand, the spectral weights of SC1 and SC2 Si-2p components in the Si-2p-Si-L23VV PEACS spectrum show a maximum peak at a relative AeKE of +3 eV. These results directly support the correlations between the five surface components (SC1-SC5) and four surface states (S1-S4) in the adatom-buckling model for the Si(110)-16 × 2 SD proposed by Sakamoto et al. [Phys. Rev. B 79, 045304 (2009)].

  6. VUV photodynamics and chiral asymmetry in the photoionization of gas phase alanine enantiomers.

    PubMed

    Tia, Maurice; Cunha de Miranda, Barbara; Daly, Steven; Gaie-Levrel, François; Garcia, Gustavo A; Nahon, Laurent; Powis, Ivan

    2014-04-17

    The valence shell photoionization of the simplest proteinaceous chiral amino acid, alanine, is investigated over the vacuum ultraviolet region from its ionization threshold up to 18 eV. Tunable and variable polarization synchrotron radiation was coupled to a double imaging photoelectron/photoion coincidence (i(2)PEPICO) spectrometer to produce mass-selected threshold photoelectron spectra and derive the state-selected fragmentation channels. The photoelectron circular dichroism (PECD), an orbital-sensitive, conformer-dependent chiroptical effect, was also recorded at various photon energies and compared to continuum multiple scattering calculations. Two complementary vaporization methods-aerosol thermodesorption and a resistively heated sample oven coupled to an adiabatic expansion-were applied to promote pure enantiomers of alanine into the gas phase, yielding neutral alanine with different internal energy distributions. A comparison of the photoelectron spectroscopy, fragmentation, and dichroism measured for each of the vaporization methods was rationalized in terms of internal energy and conformer populations and supported by theoretical calculations. The analytical potential of the so-called PECD-PICO detection technique-where the electron spectroscopy and circular dichroism can be obtained as a function of mass and ion translational energy-is underlined and applied to characterize the origin of the various species found in the experimental mass spectra. Finally, the PECD findings are discussed within an astrochemical context, and possible implications regarding the origin of biomolecular asymmetry are identified.

  7. Outermost and inner-shell electronic properties of ClC(O)SCH2CH3 studied using HeI photoelectron spectroscopy and synchrotron radiation.

    PubMed

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

    2011-06-02

    A study of valence electronic properties of S-ethyl chlorothioformate (S-ethyl chloromethanethioate), ClC(O)SCH(2)CH(3), using HeI photoelectron spectra (PES) and synchrotron radiation is presented. Moreover, the photon impact excitation and dissociation dynamics of ClC(O)SCH(2)CH(3) excited at the S 2p and Cl 2p levels are elucidated by analyzing the total ion yield (TIY) spectra and time-of-flight mass spectra acquired in multicoincidence mode [photoelectron-photoion coincidence (PEPICO) and photoelectron-photoion-photoion coincidence (PEPIPICO)]. The HeI photoelectron spectrum is dominated by features associated with lone-pair electrons from the ClC(O)S- group, the HOMO at 9.84 eV being assigned to the n(π)(S) sulfur lone-pair orbital. Whereas the formation of C(2)H(5)(+) ion dominates the fragmentation in the valence energy region, the most abundant ion formed in both the S and Cl 2p energy ranges is C(2)H(3)(+). Comparison with related XC(O)SR (X = H, F, Cl and R = -CH(3), -C(2)H(5)) species reveals the impact of the alkyl chain on the photodissociation behavior of S-alkyl (halo)thioformates. © 2011 American Chemical Society

  8. 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.

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

    SciTech Connect

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

    2015-09-10

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

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

    NASA Astrophysics Data System (ADS)

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

    2015-09-01

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

  11. 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.

  12. 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.

  13. 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.

  14. 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.

  15. Photoionization of rare gas clusters

    NASA Astrophysics Data System (ADS)

    Zhang, Huaizhen

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

  16. Electronic properties of FC(O)SCH2CH3. a combined helium(I) photoelectron spectroscopy and synchrotron radiation study.

    PubMed

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

    2014-08-07

    The valence electronic properties of S-ethyl flouromethanethioate (S-ethyl fluoromethsanethioate), FC(O)SCH2CH3, were investigated by means of He(I) photoelectron spectroscopy in conjunction with the analysis of the photofragmentation products determined by PEPICO (phtoelectron-photoion-coincidence) by using synchrotron radiation in the 11.1-21.6 eV photon energy range. The first band observed at 10.28 eV in the HeI photoelectron spectrum can be assigned with confidence to the ionization process from the HOMO [nπ(S) orbital], which is described as a lone pair formally localized on the sulfur atom, in agreement with quantum chemical calculations using the outer valence Green function method [OVGF/6-311++G (d,p)]. One of the most important fragmentation channels also observed in the valence region corresponds to the decarbonylation process yielding the [M-CO](·+) ion, which is clearly observed at m/z = 80. Moreover, S 2p and S 2s absorption edges have been examined by measuring the total ion yield spectra in the 160-240 eV region using variable synchrotron radiation. The dynamic of ionic fragmentation following the Auger electronic decay has been evaluated with the help of the PEPIPICO (photoion-photoion-photoelectron-coincidence spectra) technique.

  17. Angular and energy distribution of fragment ions in dissociative double photoionization of acetylene molecules at 39 eV

    SciTech Connect

    Alagia, M.; Callegari, C.; Richter, R.; Candori, P.; Falcinelli, S.; Vecchiocattivi, F.; Pirani, F.; Stranges, S.

    2012-05-28

    The two-body dissociation reactions of the dication, C{sub 2}H{sub 2}{sup 2+}, produced by 39.0 eV double photoionization of acetylene molecules, have been studied by coupling photoelectron-photoion-photoion coincidence and ion imaging techniques. The results provide the kinetic energy and angular distributions of product ions. The analysis of the results indicates that the dissociation leading to C{sub 2}H{sup +}+H{sup +} products occurs through a metastable dication with a lifetime of 108 {+-} 22 ns, and a kinetic energy release (KER) distribution exhibiting a maximum at {approx}4.3 eV with a full width at half maximum (FWHM) of about 60%. The reaction leading to CH{sub 2}{sup +}+C{sup +} occurs in a time shorter than the typical rotational period of the acetylene molecules (of the order of 10{sup -12} s). The KER distribution of product ions for this reaction, exhibits a maximum at {approx}4.5 eV with a FWHM of about 28%. The symmetric dissociation, leading to CH{sup +} + CH{sup +}, exhibits a KER distribution with a maximum at {approx}5.2 eV with a FWHM of 44%. For the first two reactions the angular distributions of ion products also indicate that the double photoionization of acetylene occurs when the neutral molecule is mainly oriented perpendicularly to the light polarization vector.

  18. Coincidence Measurements of Core-Excited Molecules and Clusters Using TOF Fragment-Mass Spectroscopy

    SciTech Connect

    Tabayashi, Kiyohiko; Maruyama, Tomoe; Tanaka, Kenichiro; Namatame, Hirofumi; Taniguchi, Masaki

    2007-01-19

    In order to investigate photo-induced processes and dynamics of photochemical reactions involving molecular complexes and clusters in the vacuum ultraviolet and soft X-ray region, a cluster beam-photoreactive scattering apparatus has been designed and constructed at the HiSOR facility in Hiroshima University. The apparatus has a basic arrangement of a cluster beam source and a linear time-of-flight mass spectrometer, where it was designed to give strong cluster beam intensity enough to perform a variety of photoelectron and photoion coincidence measurements. Here, we present spectroscopic and coincidence measurements of the photo-induced processes of atomic and molecular clusters in the soft X-ray region to make a fundamental assessment for the present cluster beam-photoreactive scattering apparatus.

  19. 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.

  20. Forward-backward asymmetries of atomic photoelectrons.

    SciTech Connect

    Biheux, J. C.; Dunford, R. W.; Gemmell, D. S.; Hasegawa, S.; Kanter, E. P.; Krassig, B.; Southworth, S. H.; Young, L.

    1999-01-19

    When atomic photoionization is treated beyond the dipole approximation, photoelectron angular distributions are asymmetric forward and backward with respect to the direction of the photon beam. We have measured forward-backward asymmetries of Ar 1s and Kr 1s and 2s photoelectrons using 2-19 keV x-rays. The measured asymmetries compare well with calculations which include interference between electric-dipole and electric-quadrupole amplitudes within the nonrelativistic, independent-particle approximations.

  1. 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.

  2. 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.

  3. Complete characterization of double photoionization processes

    NASA Astrophysics Data System (ADS)

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

    2011-06-01

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

  4. Complete characterization of double photoionization processes

    SciTech Connect

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

    2011-06-15

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

  5. Photoionization of aligned molecular excited states

    NASA Astrophysics Data System (ADS)

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

    1988-02-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2014-04-01

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

  7. 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)

  8. 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)

  9. 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.

  10. Unambiguous observation of F-atom core-hole localization in CF4 through body-frame photoelectron angular distributions

    NASA Astrophysics Data System (ADS)

    McCurdy, C. W.; Rescigno, T. N.; Trevisan, C. S.; Lucchese, R. R.; Gaire, B.; Menssen, A.; Schöffler, M. S.; Gatton, A.; Neff, J.; Stammer, P. M.; Rist, J.; Eckart, S.; Berry, B.; Severt, T.; Sartor, J.; Moradmand, A.; Jahnke, T.; Landers, A. L.; Williams, J. B.; Ben-Itzhak, I.; Dörner, R.; Belkacem, A.; Weber, Th.

    2017-01-01

    A dramatic symmetry breaking in K -shell photoionization of the CF4 molecule in which a core-hole vacancy is created in one of four equivalent fluorine atoms is displayed in the molecular frame angular distribution of the photoelectrons. Observing the photoejected electron in coincidence with an F+ atomic ion after Auger decay is shown to select the dissociation path where the core hole was localized almost exclusively on that atom. A combination of measurements and ab initio calculations of the photoelectron angular distribution in the frame of the recoiling CF3+ and F+ atoms elucidates the underlying physics that derives from the Ne-like valence structure of the F(1 s-1 ) core-excited atom.

  11. Unambiguous observation of F-atom core-hole localization in CF4 through body-frame photoelectron angular distributions

    DOE PAGES

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

    2017-01-17

    A dramatic symmetry breaking in K-shell photoionization of the CF4 molecule in which a core-hole vacancy is created in one of four equivalent fluorine atoms is displayed in the molecular frame angular distribution of the photoelectrons. In observing the photoejected electron in coincidence with an F+ atomic ion after Auger decay we see how selecting the dissociation path where the core hole was localized was almost exclusively on that atom. A combination of measurements and ab initio calculations of the photoelectron angular distribution in the frame of the recoiling CF3+ and F+ atoms elucidates the underlying physics that derives frommore » the Ne-like valence structure of the F(1s-1) core-excited atom.« less

  12. Nondipole effects in helium photoionization

    NASA Astrophysics Data System (ADS)

    Argenti, Luca; Moccia, Roberto

    2010-12-01

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

  13. Photoionization and photofragmentation of SF6 in helium nanodroplets.

    PubMed

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

    2006-10-12

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

  14. Photoionization of molecular clusters

    NASA Astrophysics Data System (ADS)

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

    1981-12-01

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

  15. 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.

  16. 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.

  17. A study of the photoelectron spectra of α-tetrahydrofurfuryl alcohol over the outer valence energy region (9-25 eV)

    NASA Astrophysics Data System (ADS)

    Dampc, Marcin; Mielewska, Brygida; Siggel-King, Michele R. F.; King, George C.; Zubek, Mariusz

    2017-07-01

    Photoelectron spectra of α-tetrahydrofurfuryl alcohol (THFA) molecules, the threshold spectrum and spectra for constant photoelectron energies, have been measured over the photon energy range 9-25 eV. Analysis of the photoelectron spectra has allowed overlapping photoionization bands to be separated, tentatively assigned and their vertical photoionization energies to be determined. These energies are compared with existing theoretical calculations. The photoelectron spectra indicate the predominance of one conformer in the population of gas-phase THFA.

  18. 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.

  19. 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.

  20. Mode specific photoionization dynamics in polyatomic molecules

    NASA Astrophysics Data System (ADS)

    Rathbone, Gerald Jeffery

    2002-11-01

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

  1. Photoionization of Ar VIII

    NASA Astrophysics Data System (ADS)

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

    2017-01-01

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

  2. Spin effects in double photoionization of lithium

    NASA Astrophysics Data System (ADS)

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

    2010-02-01

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

  3. 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.

  4. Channel-specific photoelectron angular distribution in laboratory and molecular frames for dissociative ionization of methanol in intense ultraviolet laser fields

    NASA Astrophysics Data System (ADS)

    Fukahori, Shinichi; Nakano, Motoyoshi; Yamanouchi, Kaoru; Itakura, Ryuji

    2017-03-01

    We investigate dissociative ionization of CH3OH in an intense laser field (398 nm, 76 fs, 8.9 × 1012 W/cm2) by photoelectron-photoion coincidence momentum imaging. It is revealed from the analysis of the channel-specific photoelectron angular distributions that CH3OH is decomposed into CH2OH+ + H after the four-photon ionization to the vibrationally highly excited states of the electronic ground state of CH3OH+ and into CH3+ + OH after the five-photon ionization to the second electronically excited state of CH3OH+, and that these two channels are also opened after CH3OH+, prepared by the four-photon ionization, is photoexcited further into the electronically excited states.

  5. 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.

  6. A new electron-ion coincidence 3D momentum-imaging method and its application in probing strong field dynamics of 2-phenylethyl-N, N-dimethylamine.

    PubMed

    Fan, Lin; Lee, Suk Kyoung; Tu, Yi-Jung; Mignolet, Benoît; Couch, David; Dorney, Kevin; Nguyen, Quynh; Wooldridge, Laura; Murnane, Margaret; Remacle, Françoise; Bernhard Schlegel, H; Li, Wen

    2017-07-07

    We report the development of a new three-dimensional (3D) momentum-imaging setup based on conventional velocity map imaging to achieve the coincidence measurement of photoelectrons and photo-ions. This setup uses only one imaging detector (microchannel plates (MCP)/phosphor screen) but the voltages on electrodes are pulsed to push both electrons and ions toward the same detector. The ion-electron coincidence is achieved using two cameras to capture images of ions and electrons separately. The time-of-flight of ions and electrons are read out from MCP using a digitizer. We demonstrate this new system by studying the dissociative single and double ionization of PENNA (2-phenylethyl-N,N-dimethylamine). We further show that the camera-based 3D imaging system can operate at 10 kHz repetition rate.

  7. A new electron-ion coincidence 3D momentum-imaging method and its application in probing strong field dynamics of 2-phenylethyl-N, N-dimethylamine

    NASA Astrophysics Data System (ADS)

    Fan, Lin; Lee, Suk Kyoung; Tu, Yi-Jung; Mignolet, Benoît; Couch, David; Dorney, Kevin; Nguyen, Quynh; Wooldridge, Laura; Murnane, Margaret; Remacle, Françoise; Bernhard Schlegel, H.; Li, Wen

    2017-07-01

    We report the development of a new three-dimensional (3D) momentum-imaging setup based on conventional velocity map imaging to achieve the coincidence measurement of photoelectrons and photo-ions. This setup uses only one imaging detector (microchannel plates (MCP)/phosphor screen) but the voltages on electrodes are pulsed to push both electrons and ions toward the same detector. The ion-electron coincidence is achieved using two cameras to capture images of ions and electrons separately. The time-of-flight of ions and electrons are read out from MCP using a digitizer. We demonstrate this new system by studying the dissociative single and double ionization of PENNA (2-phenylethyl-N,N-dimethylamine). We further show that the camera-based 3D imaging system can operate at 10 kHz repetition rate.

  8. 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.

  9. Photoelectron diffraction

    NASA Astrophysics Data System (ADS)

    Fadley, Charles S.

    1987-01-01

    The use of core-level photoelectron diffraction for structural studies of surfaces and epitaxial overlayers is discussed. Photoelectron diffraction is found to provide several direct and rather unique types of structural information, including the sites and positions of adsorbed atoms; the orientations of small molecules or fragments bound to surfaces; the orientations, layer thicknesses, vertical lattice constants, and degrees of short-range order of epitaxial or partially-epitaxial overlayers; and the presence of short-range spin order in magnetic materials. Specific systems considered are the reaction of oxygen with Ni(001), the growth of epitaxial Cu on Ni(001), the well-defined test case S on Ni(001), and short-range spin order in the antiferromagnet KMnF3. A rather straightforward single scattering cluster (SSC) model also proves capable of quantitatively describing such data, particularly for near-surface species and with corrections for spherical-wave scattering effects and correlated vibrational motion. Promising new directions in such studies also include measurements with high angular resolution and the expanded use of synchrotron radiation.

  10. Dynamics of electron emission in double photoionization processes near the krypton 3d threshold

    NASA Astrophysics Data System (ADS)

    Penent, F.; Sheinerman, S.; Andric, L.; Lablanquie, P.; Palaudoux, J.; Becker, U.; Braune, M.; Viefhaus, J.; Eland, J. H. D.

    2008-02-01

    Two-electron emission following photoabsorption near the Kr 3d threshold is investigated both experimentally and theoretically. On the experimental side, electron/electron coincidences using a magnetic bottle time-of-flight spectrometer allow us to observe the complete double photo ionization (DPI) continua of selected Kr2+ final states, and to see how these continua are affected by resonant processes in the vicinity of the Kr 3d threshold. The analysis is based on a quantum mechanical approach that takes into account the contribution of three different processes: (A) Auger decay of the inner 3d vacancy with the associated post-collision interaction (PCI) effects, (B) capture of slow photoelectrons into discrete states followed by valence multiplet decay (VMD) of the excited ionic states and (C) valence shell DPI. The dominant process for each Kr2+(4p-2) final state is the photoionization of the inner shell followed by Auger decay of the 3d vacancies. Moreover, for the 4p-2(3P) and 4p-2(1D) final ionic states an important contribution comes from the processes of slow photoelectron capture followed by VMD as well as from double ionization of the outer shell involving also VMD.

  11. Flash-photoionized nebulae

    NASA Technical Reports Server (NTRS)

    Katz, J. I.

    1989-01-01

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

  12. Flash-photoionized nebulae

    SciTech Connect

    Katz, J.I.

    1989-05-01

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

  13. Double Photoionization Near Threshold

    NASA Technical Reports Server (NTRS)

    Wehlitz, Ralf

    2007-01-01

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

  14. 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.

  15. Direct experimental evidence for dissociative photoionization of oxygen molecule via 2Σ(u)(-) ionic "optical dark" state.

    PubMed

    Tang, Xiaofeng; Zhou, Xiaoguo; Wu, Manman; Cai, Yu; Liu, Shilin; Sheng, Liusi

    2012-09-27

    Direct experimental evidence for dissociative photoionization of oxygen molecule via the (2)Σ(u)(-) ionic optical dark state is presented by an investigation using the method of threshold photoelectron-photoion coincidence (TPEPICO) velocity imaging. Besides vibrational progress of the B(2)Σ(g)(-) state, several weak vibrational bands of the (2)Σ(u)(-) ionic optical dark state are observed concomitantly in an excitation energy range of 20.2-21.1 eV. Only O(+) fragments are detected in the whole excitation energy range; therefore, all vibrational bands are completely predissociative. TPEPICO three-dimensional time-sliced velocity images of O(+) fragments dissociated from vibrational state-selected O(2)(+)((2)Σ(u)(-),v(+)) ions are recorded. For the (2)Σ(u)(-)(v(+)=0-3) vibrational states, only the lowest dissociation channel of O(+)((4)S) + O((3)P) is observed. Once the photon energy is slightly increased to the (2)Σ(u)(-)(v(+)=4) level, a new concentric doughnut appears in the image, indicating that the second dissociation channel of O(+)((4)S) + O((1)D) is identified indeed. With the aid of potential energy curves, the dissociative mechanism of O(2)(+) in the (2)Σ(u)(-)(v(+)) state is proposed.

  16. 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.

  17. 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

    2009-06-05

    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.

  18. 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.

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

    NASA Astrophysics Data System (ADS)

    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.

  20. Photoelectron Microscopy

    NASA Astrophysics Data System (ADS)

    King, Paul Lawrence

    1992-01-01

    This thesis describes the theory and first operations of a novel synchrotron-based imaging system allowing photoemission spectroscopy (XPS or ESCA) to be performed at lateral resolutions better than 10 microns. Originally developed in David Turner's group at Oxford, the MicroESCA^ {rm TM} relies on the diverging magnetic field from a 7 Tesla superconducting solenoid to project photoemitted electrons from a sample to an imaging detector located 1.5 meters away. The diverging magnetic field converts off-axis momentum to forward momentum and electrons form a magnified image at the detector while moving nearly parallel to one another. Because of this "parallelization", a planar gridded retarding field analyzer achieves excellent energy resolution with only minor impact on image quality. The thesis begins with an overview of the various techniques by which high lateral resolution photoelectron spectroscopy can be achieved. This is followed by a theoretical treatment of magnetic projection leading to predictions of lateral and energy resolution. Chapter 3 documents resolution tests and known deviations from ideality. Image forming capabilities and energy resolution of the retarding field analyzer are demonstrated at near-theoretical limits. Practical limitations of the microscope are recognized in the form of poor signal to noise ratios of core level images which originate from a combination of the narrow dynamic range of the imaging detector and the large backgrounds inherent in retarding field spectroscopy of solids. Chapter 4 describes an interactive image processing and interpretation scheme that relies on scatter plots and principal component analysis to reduce the dimensionality of retarding field image sets and improve image signal to noise. This procedure is generally applicable to all imaging spectroscopies and an example from SEM-based energy dispersive spectroscopy (EDS) is included. In a final results section, variations in the surface Fermi levels on cleaved

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

    PubMed

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

    2016-06-09

    The unimolecular dissociation of energy-selected ethylenediamine cations was studied by threshold photoelectron photoion coincidence spectroscopy (TPEPICO) in the photon energy range of 8.60-12.50 eV. Modeling the breakdown diagram and time-of-flight distributions with rigid activated complex RRKM theory yielded 0 K appearance energies for eight dissociation channels, leading to NH2CHCH2(+)(•) at 9.120 ± 0.010 eV, CH3C(NH2)2(+) at 9.200 ± 0.012 eV, NH2CHCH3(+) at 9.34 ± 0.08 eV, CH2NH2(+) at 9.449 ± 0.025 eV, CH2NH3(+) at 9.8 ± 0.1 eV, c-C2H4NH2(+) at 10.1 ± 0.1 eV, CH3NHCHCH2(+) at 10.2 ± 0.1 eV, and the reappearance of CH2NH2(+) at 10.2 ± 0.1 eV. The CBS-QB3-calculated pathways highlighted the influence of intramolecular hydrogen attractions on the dissociation processes, presenting novel isomers and low-energy van der Waals intermediates that led to fragments in good agreement with experimental results. While most of the dissociation channels take place through reverse barriers, the 0 K heat of formation of (•)CH2NH2 was determined to be 147.6 ± 3.7 kJ mol(-1), in excellent agreement with literature, and the 0 K heat of formation of CH2NH3(+) at 844 ± 10 kJ mol(-1) is the first experimentally measured value available and is in good agreement with theory.

  2. 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.

  3. Angular-momentum transfer due to postcollision interaction in atomic inner n s2 -shell photoionization

    NASA Astrophysics Data System (ADS)

    Gerchikov, L.; Guillemin, R.; Simon, M.; Sheinerman, S.

    2017-06-01

    A concrete mechanism of angular-momentum transfer in photoionization process is proposed for electron photoemission from deep inner atomic shells. It is demonstrated that the leading contribution to angular-momentum transfer is provided by postcollision interaction of the photoelectrons and Auger electrons. The standard theoretical approach to postcollision interaction has been considerably improved by taking into account angular-momentum transfer. The theory developed is applied to the photoionization of 1 s2 shell in Ar. Calculations show the noticeable influence of angular-momentum transfer on the photoelectron angular distribution.

  4. Uncovering Highly-Excited State Mixing in Acetone Using Ultrafast VUV Pulses and Coincidence Imaging Techniques

    DOE PAGES

    Couch, David E.; Kapteyn, Henry C.; Murnane, Margaret M.; ...

    2017-03-17

    Here, understanding the ultrafast dynamics of highly-excited electronic states of small molecules is critical for a better understanding of atmospheric and astrophysical processes, as well as for designing coherent control strategies for manipulating chemical dynamics. In highly excited states, nonadiabatic coupling, electron-electron interactions, and the high density of states govern dynamics. However, these states are computationally and experimentally challenging to access. Fortunately, new sources of ultrafast vacuum ultraviolet pulses, in combination with electron-ion coincidence spectroscopies, provide new tools to unravel the complex electronic landscape. Here we report time-resolved photoelectron-photoion coincidence experiments using 8 eV pump photons to study the highlymore » excited states of acetone. We uncover for the first time direct evidence that the resulting excited state consists of a mixture of both ny → 3p and π → π* character, which decays with a time constant of 330 fs. In the future, this approach can inform models of VUV photochemistry and aid in designing coherent control strategies for manipulating chemical reactions.« less

  5. 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.

  6. Threshold photoelectron study of naphthalene, anthracene, pyrene, 1,2-dihydronaphthalene, and 9,10-dihydroanthracene

    NASA Astrophysics Data System (ADS)

    Mayer, Paul M.; Blanchet, Valerie; Joblin, Christine

    2011-06-01

    Threshold photoelectron spectra (TPESs) were obtained for naphthalene, anthracene, pyrene, 1,2-dihydronaphthalene, and 9,10-dihydroanthracene using imaging photoelectron photoion coincidence spectroscopy, from threshold to a photon energy of ˜20 eV. Outer valence Green's function calculations at the OVGF/cc-pVTZ level of theory were used to assign molecular orbitals to the observed TPES features. There is generally good agreement between the predicted and observed bands. Threshold regions for each molecule exhibit vibrational structure which is readily assigned based on previous PES studies. While the measured adiabatic ionization energies (IEa) for naphthalene, anthracene, and pyrene are in good agreement with previous works, new values are reported for the two dihydro species (1,2-dihydronaphthalene, 8.010 ± 0.010 eV and 9,10-dihydroanthracene, 8.335 ± 0.010 eV). A comparison is also made with the G3//B3LYP composite method, which consistently overestimates the IE values by 0.06-0.09 eV. The double ionization energies for anthracene and pyrene have been measured to be 19.3 ± 0.2 and 19.8 ± 0.2 eV, respectively.

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

    NASA Astrophysics Data System (ADS)

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

    2001-03-01

    We present results on the energy dependence of the vibrational branching ratio for the bending mode in CO2 3σu-1 photoionization. Specifically, we determine the v+=(0,1,0)/v+=(0,0,0) intensity ratio by detecting dispersed fluorescence from the electronically excited photoions. The results exhibit large deviations over a very wide energy range, 18photoelectron spectroscopy, their appearance is normally ascribed to vibronic coupling in the ionic hole state. In this case, we find that such explanations fail to account for the energy dependence of the branching ratio. These deviations indicate that the continuum photoelectron participates in transferring oscillator strength to the nominally forbidden vibrational transition. A theoretical framework is developed for interpreting the experimental data, and Schwinger variational calculations are performed. These calculations demonstrate that the continuum electron is responsible for the observation of the excited bending mode as well as its energy dependence. This is an intrachannel effect that is best described as photoelectron-induced vibronic symmetry breaking. This appears to be a general phenomenon, and it may be useful in illuminating connections between bond angle and photoionization spectroscopies. The magnitude of these deviations display the utility of vibrationally resolved studies, and the extent over which these changes occur underscores the necessity of broad range studies to elucidate slowly varying characteristics in photoionization continua.

  8. Photoelectron spectroscopy of supersonic molecular beams

    SciTech Connect

    Pollard, J.E.

    1982-05-01

    A new technique for performing high resolution molecular photoelectron spectroscopy is described, beginning with its conceptual development, through the construction of a prototypal apparatus, to the initial applications on a particularly favorable molecular system. The distinguishing features of this technique are: (1) the introduction of the sample in the form of a collimated supersonic molecular beam; and (2) the use of an electrostatic deflection energy analyzer which is carefully optimized in terms of sensitivity and resolution. This combination makes it possible to obtain photoelectron spectra at a new level of detail for many small molecules. Three experiments are described which rely on the capability to perform rotationally-resolved photoelectron spectroscopy on the hydrogen molecule and its isotopes. The first is a measurement of the ionic vibrational and rotational spectroscopic constants and the vibrationally-selected photoionization cross sections. The second is a determination of the photoelectron asymmetry parameter, ..beta.., for selected rotational transitions. The third is an investigation of the rotational relaxation in a free jet expansion, using photoelectron spectroscopy as a probe of the rotational state population distributions. In the closing chapter an assessment is made of the successes and limitations of the technique, and an indication is given of areas for further improvement in future spectrometers.

  9. Photodetachment and photoionization rainbows and glories

    NASA Astrophysics Data System (ADS)

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

    2017-03-01

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

  10. Photoionization of the Buckminsterfullerene Cation.

    PubMed

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

    2017-01-05

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

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

    NASA Astrophysics Data System (ADS)

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

    2007-06-01

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

  12. Photoionization of FE3+ Ions

    SciTech Connect

    Ovchinnikov, O.; Schlachter, F.

    2003-01-01

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

  13. Photoelectron circular dichroism in different ionization regimes

    NASA Astrophysics Data System (ADS)

    Wollenhaupt, Matthias

    2016-12-01

    Photoelectron circular dichroism (PECD) describes an asymmetry in the photoelectron angular distribution (PAD) from photoionization of randomly oriented enantiomers with circularly polarized light. Beaulieu et al present a comprehensive set of measured PADs from multiphoton ionization of limonene and fenchone in different ionization regimes (multiphoton and tunneling) and analyze the resulting PECD (Beaulieu et al 2016 New J. Phys. 18 102002). From their observations the authors conclude that the PECD is universal in the sense that the molecular chirality is encoded in the PAD independent of the ionization regime. The analysis is supplemented by a classical model based on electron scattering in a chiral potential. The paper presents beautiful data and is an important step towards a more complete physical picture of PECD. The results and their interpretation stimulate the ongoing vivid debate on the role of resonances in multiphoton PECD.

  14. Photoionization of hydrogen-like ions in dense quantum plasmas

    NASA Astrophysics Data System (ADS)

    Qi, Y. Y.; Wang, J. G.; Janev, R. K.

    2017-06-01

    The photoionization of hydrogen-like ions in n ≤ 3 bound states, embedded in cold, dense quantum plasmas, is investigated in detail. The electron energies and wave functions for the bound and continuum states are determined by numerically solving the scaled Schrödinger equation by the fourth-order symplectic integration scheme. The monotonic behavior of the photoionization cross section for a pure Coulomb potential is dramatically changed due to the plasma screening effects described by the cosine-Debye-Hückel potential. In the region of low photoelectron energies, the photoionization cross section, besides the usual Wigner-law threshold behavior, exhibits a rich structure of shape and virtual-state resonances when the plasma screening parameter takes values around the critical screening parameter for which a bound state enters the continuum. It is observed that a shape resonance is followed by a Cooper minimum in the photoionization cross section when the principal quantum number of continuum quasi-bound state is equal to the one of the initial bound states.

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

    PubMed

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

    2009-12-14

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

  16. High-efficiency photoionization detector

    SciTech Connect

    Anderson, D.F.

    1981-05-12

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

  17. Angular and energy distributions of fragment ions in dissociative double photoionization of acetylene molecules in the 31.9-50.0 eV photon energy range

    NASA Astrophysics Data System (ADS)

    Falcinelli, Stefano; Alagia, Michele; Farrar, James M.; Kalogerakis, Konstantinos S.; Pirani, Fernando; Richter, Robert; Schio, Luca; Stranges, Stefano; Rosi, Marzio; Vecchiocattivi, Franco

    2016-09-01

    The two-body dissociation reactions of the dication C2H2+2, initiated via double ionization of acetylene molecules by photons in the energy range 31.9-50.0 eV, have been studied by coupling photoelectron-photoion-photoion coincidence and ion imaging techniques. The angular distributions and kinetic energy of product ions, measured in the 31.9-50.0 eV energy range, exhibit significant differences for the three leading dissociation reactions with respect to a previous investigation carried out at a fixed energy of 39.0 eV, providing thus new information on the dynamical evolution of the system. The analysis of the results indicates that such dissociation reactions occur with a different mechanism. In particular, the symmetric dissociation in two CH+ ions is characterized by different dynamics, and the anisotropy of the angular distribution of ionic products increases with photon energy in a more pronounced way than the other two reactions. Moreover, the kinetic energy distribution of the symmetric dissociation reaction exhibits several components that change with photon energy. The new experimental findings cast light on the microscopic evolution of the system and can provide a laboratory reference for new theoretical calculations on specific features of the multidimensional potential energy surface, namely, the structure, energy and symmetry of dication states, the electronic state of dissociation products, energy barriers and their dependence on the geometry of the intermediate state.

  18. 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.

  19. Evolution of photoelectron vibrational coupling with molecular complexity

    NASA Astrophysics Data System (ADS)

    Poliakoff, E. D.; Lucchese, R. R.

    2006-11-01

    We review how electronic and vibrational degrees of freedom become coupled in molecular photoionization, and describe effects that emerge as the molecular complexity increases. Molecular photoionization is frequently influenced by the temporary trapping of the continuum electron in the field of the target molecules, which is referred to as a shape resonance, as it depends on the shape of the potential experienced by the exiting photoelectron. Such resonances couple electronic and vibrational motion, and the nature of the coupling can vary widely for polyatomic molecules. We show how vibrationally resolved photoelectron spectra acquired as a function of energy can be used to elucidate such coupling. The experiments are analysed using physically realistic and computationally tractable Schwinger variational theory, and the systems studied to date can be well understood using an independent-particle, adiabatic nuclei framework. As a result, simple and intuitive pictures emerge, even when dealing with scattering phenomena involving complex molecular targets and potentials.

  20. Photoionization of Endohedral Atoms: Collective, Reflective and Collateral Emissions

    NASA Astrophysics Data System (ADS)

    Chakraborty, Himadri S.; McCune, Matthew A.; Madjet, Mohamed E.; Hopper, Dale E.; Manson, Steven T.

    2009-12-01

    The photoionization properties of a fullerene-confined atom differ dramatically from that of an isolated atom. In the low energy region, where the fullerene plasmons are active, the electrons of the confined atom emerge through a collective channel carrying a significant chunk of plasmon with it. The photoelectron angular distribution of the confined atom however shows far lesser impact of the effect. At higher energies, the interference between two single-electron ionization channels, one directly from the atom and another reflected off the fullerene cage, producuces oscillatory cross sections. But for the outermost atomic level, which transfers some electrons to the cage, oscillations are further modulated by the collateral emission from the part of the atomic charge density transferred to the cage. These various modes of emissions are studied for the photoionization of Ar endohedrally confined in C60.

  1. 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.

  2. 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}.

  3. Photoionization of sodium clusters

    SciTech Connect

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

    1984-03-01

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

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

    NASA Astrophysics Data System (ADS)

    Braunstein, M.; McKoy, V.

    1989-02-01

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

  5. High-resolution threshold photoelectron spectroscopy by electron attachment

    NASA Technical Reports Server (NTRS)

    Ajello, J. M.; Chutjian, A.

    1976-01-01

    A new technique for measuring high-resolution threshold photoelectron spectra of atoms, molecules, and radicals is described. It involves photoionization of a gaseous species, attachment of the threshold, or nearly zero electron to some trapping molecule (here SF6 or CFCl3), and mass detection of the attachment product (SF6/-/ or Cl/-/ respectively). This technique of threshold photoelectron spectroscopy by electron attachment was used to measure the spectra of argon and xenon at 11 meV (FWHM) resolution, and was also applied to CFCl3.

  6. Spectra of resonance surface photoionization

    SciTech Connect

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

    1995-09-01

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

  7. 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.

  8. 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.

  9. Relaxation effects in inner-shell photoionization of Mg, Ca, and Sr

    NASA Astrophysics Data System (ADS)

    Kutzner, M.; Maycock, V.; Thorarinson, J.; Pannwitz, E.; Robertson, J. A.

    2002-10-01

    Total and partial photoionization cross sections have been calculated for all inner subshells of atomic magnesium, calcium, and strontium in the relativistic random-phase approximation, the relativistic random-phase approximation modified to include relaxation effects, and the relativistic random-phase approximation modified to include relaxation and Auger decay. Results of the three models are compared with Dirac-Hartree-Fock calculations and with semiempirical results so that the import of various many-body effects can be assessed. Branching ratios and photoelectron angular-distribution asymmetry parameters are also presented for np subshells. Substantial relaxation effects are noted for photoionization of 1s and 2s subshells.

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

    NASA Astrophysics Data System (ADS)

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

    1994-01-01

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

  11. The role of photoionization in negative corona discharge: The influences of temperature, humidity, and air pressure on a corona

    NASA Astrophysics Data System (ADS)

    Sun, H. Y.; Lu, B. X.; Wang, M.; Guo, Q. F.; Feng, Q. K.

    2017-10-01

    The swarm parameters of the negative corona discharge are improved to calculate the discharge model under different environmental conditions. The effects of temperature, humidity, and air pressure are studied using a conventional needle-to-plane configuration in air. The electron density, electric field, electron generation rate, and photoelectron generation rate are discussed in this paper. The role of photoionization under these conditions is also studied by numerical simulation. The photoelectrons generated in weak ionization region are proved to be dominant.

  12. 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.

  13. Vibrationally Resolved B 1s Photoionization Cross Section of BF3.

    PubMed

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

    2015-06-11

    Photoelectron diffraction is a well-established technique for structural characterization of solids, based on the interference of the native photoelectron wave with those scattered from the neighboring atoms. For isolated systems in the gas phase similar studies suffer from orders of magnitude lower signals due to the very small sample density. Here we present a detailed study of the vibrationally resolved B 1s photoionization cross section of BF3 molecule. A combination of high-resolution photoelectron spectroscopy measurements and of state-of-the-art static-exchange and time-dependent DFT calculations shows the evolution of the photon energy dependence of the cross section from a complete trapping of the photoelectron wave (low energies) to oscillations due to photoelectron diffraction phenomena. The diffraction pattern allows one to access structural information both for the ground neutral state of the molecule and for the core-ionized cation. Due to a significant change in geometry between the ground and the B 1s(-1) core-ionized state in the BF3 molecule, several vibrational final states of the cation are populated, allowing investigation of eight different relative vibrationally resolved photoionization cross sections. Effects due to recoil induced by the photoelectron emission are also discussed.

  14. 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.

  15. Decoherence in attosecond photoionization.

    PubMed

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

    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.

  16. 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.

  17. The Study of State-Selected Ion-Molecule Reactions using the Vacuum Ultraviolet Pulsed Field Ionization-Photoion Technique

    DTIC Science & Technology

    2006-01-01

    reactant ion preparation is the photoelectron-photoion coin- spheric, industrial, and aerospace plasmas .17-21 It is known cidence technique, which...Phys. 34, 43 (1999). 55 K. Norwood and C. Y. Ng. Chem. Phys. Lett. 156, 145 (1989). 16R. A. Dressier and A. A. Viggiano , in The Encyclopedia of Mass

  18. 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.

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

    SciTech Connect

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

    1981-11-01

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

  20. 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.

  1. Photoionization and electron-ion recombination of P II

    NASA Astrophysics Data System (ADS)

    Nahar, Sultana N.

    2017-08-01

    A study of the inverse processes of photoionization and electron-ion recombination of P ii is reported. Phosphorus, a little studied cosmic element, requires atomic parameters such as those presented here for spectral analysis. The unified method of Nahar and Pradhan, which incorporates two methods of recombination - radiative recombination (RR) and dielectronic recombination (DR) - and the interference between them, is used to obtain the total electron-ion recombination. This method implements the framework of the {R}-matrix close-coupling approximation. The present results include the partial photoionization cross-sections σPI(Jπ) leaving the residual ion in the ground level and level-specific recombination rate coefficients, αRC(Jπ), of 475 fine-structure levels of P ii with n ≤10. In photoionization of the ground and many excited levels, a sharp resonance is found to form at the ionization threshold from couplings of relativistic fine-structure channels. These, with other resonances in the near-threshold energy region, yield a slight curvature, in contrast to typical smooth decay, at a very low temperature of about 330 K in the total recombination rate coefficient αRC. The presence of other Rydberg and Seaton resonances in the photoionization cross-section introduces features in the level-specific recombination rate coefficients and a DR bump at high temperature at 105 K for the total recombination rate coefficient. Considerable interference between RR and DR is noted around 6700 K. The recombination spectrum with respect to photoelectron energy αRC(E) is also presented. The results are expected to provide accurate models for astrophysical plasmas up to ∼1 MK.

  2. What can we Learn on Gas Phase Chiral Compounds by Photoelectron Circular Dichroism ?

    NASA Astrophysics Data System (ADS)

    Nahon, Laurent

    2017-06-01

    Since 15 years, a new type of chiroptical effect has been the subject of a large array of both theoretical and experimental studies: Photoelectron Circular Dichroism (PECD) in the angular distribution of photoelectrons produced by CPL-ionization of pure enantiomers in the gas phase observed as a very intense (up to 35 %) forward/backward asymmetry with respect to the photon axis and which reveals the chirality of the molecule (configuration). PECD happens to be an orbital-specific, photon energy dependent effect and is a very subtle probe of the molecular potential being very sensitive to static molecular structures such as conformers, chemical substitution, clusters, as well as to vibrational motion, much more so than other observables in photoionization such as the cross section or the β asymmetry parameter (for a recent review see L. Nahon, G. A. Garcia, and I. Powis, J. Elec. Spec. Rel. Phen. 204, 322 (2015)). Therefore PECD studies have both a fundamental interest as well and analytical interest, especially since chiral species are ubiquitous in the biosphere, food and medical industry. This last aspect is probably the driving force for the recent extension of PECD studies by the laser community using UV REMPI schemes. After a large introduction to the PECD process itself, and a description of our double imaging electron/ion coincidence set-up, several recent results on one-photon VUV PECD will be presented, including: - Sensitivity to chemical substitutions, isomerism and conformation - Case of floppy biomolecules such as amino acids alanine and proline with a conformer analysis and possible consequences for the origin of life's homochirality - Analytical capabilities in terms of enantiomeric excess determination on a pure molecule as well as on a mixture of compounds. Future trends for PECD studies will be given regarding the case of more complex/structured chiral systems as well as opportunities for time-resolved PECD opened by the recent first performance

  3. Intramolecular photoelectron diffraction in the gas phase

    NASA Astrophysics Data System (ADS)

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

    2013-09-01

    We report unambiguous experimental and theoretical evidence of intramolecular photoelectron diffraction in the collective vibrational excitation that accompanies high-energy photoionization of gas-phase CF4, BF3, and CH4 from the 1s orbital of the central atom. We show that the ratios between vibrationally resolved photoionization cross sections (v-ratios) exhibit pronounced oscillations as a function of photon energy, which is the fingerprint of electron diffraction by the surrounding atomic centers. This interpretation is supported by the excellent agreement between first-principles static-exchange and time-dependent density functional theory calculations and high resolution measurements, as well as by qualitative agreement at high energies with a model in which atomic displacements are treated to first order of perturbation theory. The latter model allows us to rationalize the results for all the v-ratios in terms of a generalized v-ratio, which contains information on the structure of the above three molecules and the corresponding molecular cations. A fit of the measured v-ratios to a simple formula based on this model suggests that the method could be used to obtain structural information of both neutral and ionic molecular species.

  4. Intramolecular photoelectron diffraction in the gas phase.

    PubMed

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

    2013-09-28

    We report unambiguous experimental and theoretical evidence of intramolecular photoelectron diffraction in the collective vibrational excitation that accompanies high-energy photoionization of gas-phase CF4, BF3, and CH4 from the 1s orbital of the central atom. We show that the ratios between vibrationally resolved photoionization cross sections (v-ratios) exhibit pronounced oscillations as a function of photon energy, which is the fingerprint of electron diffraction by the surrounding atomic centers. This interpretation is supported by the excellent agreement between first-principles static-exchange and time-dependent density functional theory calculations and high resolution measurements, as well as by qualitative agreement at high energies with a model in which atomic displacements are treated to first order of perturbation theory. The latter model allows us to rationalize the results for all the v-ratios in terms of a generalized v-ratio, which contains information on the structure of the above three molecules and the corresponding molecular cations. A fit of the measured v-ratios to a simple formula based on this model suggests that the method could be used to obtain structural information of both neutral and ionic molecular species.

  5. Observation of the Symmetry-Forbidden 5σu→kσu CS2 Transition: A Vibrationally Driven Photoionization Resonance

    NASA Astrophysics Data System (ADS)

    Rathbone, G. J.; Poliakoff, E. D.; Bozek, John D.; Lucchese, R. R.

    2004-04-01

    Vibrationally resolved photoelectron spectroscopy and Schwinger calculations are used to characterize a new resonance phenomenon in the 5σu→kσu photoionization of CS2. This resonant channel is symmetry forbidden, yet is observable because it is activated by the antisymmetric stretching vibration. In addition, we show that a Franck-Condon breakdown occurs even though the energy dependence of the cross section is insensitive to geometry changes, which is unprecedented in photoionization.

  6. Vacuum ultraviolet photoionization study of gas phase vitamins A and B1 using aerosol thermodesorption and synchrotron radiation.

    PubMed

    Dossmann, Héloïse; Schwarzenberg, Adrián; Lesage, Denis; Pérot-Taillandier, Marie; Afonso, Carlos; Cunha de Miranda, Barbara; Garcia, Gustavo A

    2014-11-26

    Gas-phase studies of biomolecules are often difficult to initiate because of the thermolability of these systems. Such studies are nevertheless important to determine fundamental intrinsic properties of the molecules. Here we present the valence shell photoionization of gas-phase vitamins A and B1 close to their ionization threshold. The study was performed by means of an aerosol thermodesorption source coupled to an electron/ion coincidence spectrometer and synchrotron radiation (SOLEIL facility, France). Ion yield curves were recorded for both molecules over a few electronvolt energy range and the threshold photoelectron spectrum was also obtained for vitamin A. Some fundamental properties were extracted for both ions such as adiabatic and the three first vertical ionization energies of retinol (IEad = 6.8 ± 0.2 eV and IEvert = 7.4, 8.3, and 9.2 eV) and dissociation appearance energies for the main fragment ions of vitamin B1. Analysis of the data was supported by ab initio calculations which show a very good agreement with the experimental observations.

  7. 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)

  8. 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)

  9. PHOTOIONIZATION IN THE SOLAR WIND

    SciTech Connect

    Landi, E.; Lepri, S. T.

    2015-10-20

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

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

    SciTech Connect

    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 Li{sub 2−8} 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 Li{sub 2} are in a good agreement with the available theoretical data, whereas those computed for Li{sub 3−8} clusters can be considered as theoretical predictions.

  11. 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.

  12. 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

    NASA Astrophysics Data System (ADS)

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

    2009-05-01

    The (VA +, Ve, 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 βC+/O+ and βe asymmetry parameters as well as the relative branching ratios in selected binding energy bands. The I(χ,θe,φe) 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.

  13. 4f photoionization and subsequent Auger decay in atomic Pb: Relativistic effects

    SciTech Connect

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

    2011-05-15

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

  14. 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.

  15. 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.

  16. Valence photoionization and resonant Auger decay of Sb{sub 4} clusters at resonances below the 4d ionization threshold

    SciTech Connect

    Urpelainen, S.; Niskanen, J.; Kettunen, J. A.; Huttula, M.; Aksela, H.

    2011-01-15

    The valence photoionization and resonant Auger decay at 4d resonances below the 4d ionization threshold in Sb{sub 4} clusters have been studied experimentally by means of photoelectron spectroscopy. The 4d absorption spectrum in the photon energy region from 30 to 36 eV has been recorded using the constant ionic state (CIS) partial electron yield (PEY), and the CIS spectra for various ionic states are presented. The photoelectron spectra at various resonant positions are recorded, and the results and their interpretation are presented. The findings provide experimental proof of the previous assignment of the various structures of the inner valence photoelectron spectrum.

  17. Revealing Deactivation Pathways Hidden in Time-Resolved Photoelectron Spectra

    NASA Astrophysics Data System (ADS)

    Ruckenbauer, Matthias; Mai, Sebastian; Marquetand, Philipp; González, Leticia

    2016-10-01

    Time-resolved photoelectron spectroscopy is commonly employed with the intention to monitor electronic excited-state dynamics occurring in a neutral molecule. With the help of theory, we show that when excited-state processes occur on similar time scales the different relaxation pathways are completely obscured in the total photoionization signal recorded in the experiment. Using non-adiabatic molecular dynamics and Dyson norms, we calculate the photoionization signal of cytosine and disentangle the transient contributions originating from the different deactivation pathways of its tautomers. In the simulations, the total signal from the relevant keto and enol tautomers can be decomposed into contributions either from the neutral electronic state populations or from the distinct mechanistic pathways across the multiple potential surfaces. The lifetimes corresponding to these contributions cannot be extracted from the experiment, thereby illustrating that new experimental setups are necessary to unravel the intricate non-adiabatic pathways occurring in polyatomic molecules after irradiation by light.

  18. Revealing Deactivation Pathways Hidden in Time-Resolved Photoelectron Spectra

    PubMed Central

    Ruckenbauer, Matthias; Mai, Sebastian; Marquetand, Philipp; González, Leticia

    2016-01-01

    Time-resolved photoelectron spectroscopy is commonly employed with the intention to monitor electronic excited-state dynamics occurring in a neutral molecule. With the help of theory, we show that when excited-state processes occur on similar time scales the different relaxation pathways are completely obscured in the total photoionization signal recorded in the experiment. Using non-adiabatic molecular dynamics and Dyson norms, we calculate the photoionization signal of cytosine and disentangle the transient contributions originating from the different deactivation pathways of its tautomers. In the simulations, the total signal from the relevant keto and enol tautomers can be decomposed into contributions either from the neutral electronic state populations or from the distinct mechanistic pathways across the multiple potential surfaces. The lifetimes corresponding to these contributions cannot be extracted from the experiment, thereby illustrating that new experimental setups are necessary to unravel the intricate non-adiabatic pathways occurring in polyatomic molecules after irradiation by light. PMID:27762396

  19. Identification of photoelectron energy peaks in Saturn's inner neutral torus

    NASA Astrophysics Data System (ADS)

    Schippers, P.; André, N.; Johnson, R. E.; Blanc, M.; Dandouras, I.; Coates, A. J.; Krimigis, S. M.; Young, D. T.

    2009-12-01

    We present observations from the Cassini Plasma Electron Spectrometer (CAPS/ELS) of characteristic peaks in the electron energy spectrum that are identified in the innermost regions of the Saturnian magnetosphere during low-latitude orbits of the Cassini spacecraft around Saturn. We show how a narrow electron energy peak at about 20 eV and a possible peak at about 42 eV can be extracted from the background in CAPS observations after the contamination from high-energy particles has been removed from the measurements. We estimate the density of the newly discovered electron population to be a small fraction (10%) of the electron density measured in the CAPS/ELS energy range, and a much smaller fraction (about 1%) of the total electron density measured by Radio and Plasma Wave Science since our measurements are affected by spacecraft negative potential. We suggest that this population corresponds to photoelectrons generated by the solar EUV photoionization of the extended cloud of neutral gas observed in these regions. We use pitch angle information to assess the near-equatorial source of these photoelectrons and a simple model of chemistry in order to further support our interpretation. Therefore, photoionization seems to be an additional process for plasma production in the innermost Saturnian magnetosphere. Finally, we mention that the comparison of the modeled and the observed photoelectron peak energies could be used to estimate the spacecraft potential in this region which is measured independently by the Langmuir Probe.

  20. Photoionization of oxidized metal clusters

    SciTech Connect

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

    1984-01-01

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

  1. Graphene Membranes for Atmospheric Pressure Photoelectron Spectroscopy.

    PubMed

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

    2016-05-05

    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.

  2. Vibrationally mode-specific excitation in molecular photoionization

    NASA Astrophysics Data System (ADS)

    Poliakoff, Erwin

    2003-05-01

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

  3. 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.

  4. 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.

  5. 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

  6. Triple Coincidence Radioxenon Detector

    SciTech Connect

    McIntyre, Justin I.; Aalseth, Craig E.; Bowyer, Ted W.; Hayes, James C.; Heimbigner, Tom R.; Morris, Scott J.; Reeder, Paul L.

    2004-09-22

    The Automated Radioxenon Sampler/Analyzer (ARSA) built by Pacific Northwest National Laboratory (PNNL) is on e of the world’s most sensitive systems for monitoring the four radioxenon isotopes 133Xe, 133mXE, 131mXe and 135Xe. However, due to size, weight and power specifications appropriate to meet treaty-monitoring requirements; the ARSA is unsuitable for rapid deployment using modest transportation means. To transition this technology to a portable unit can be easily and rapidly deployed can be achieved by significant reductions in size, weight and power consumption if concentration were not required. As part of an exploratory effort to reduce both the size of the air sample and the gas processing requirement PNNL has developed an experimental nuclear detector to test and qualify the use of triple coincidence signatures (beta, conversion electron, x-ray) from two of the radioxenon isotopes (135Xe and 133Xe) as well as the more traditional beta-gamma coincidence signatures used by the ARSA system. The additional coincidence requirement allows for reduced passive shielding, and makes it possible for unambiguous detection of 133Xe and 153Xe in the presence of high 222Rn backgrounds. This paper will discuss the experimental setup and the results obtained for a 133Xe sample with and without 222Rn as an interference signature.

  7. 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.

  8. Compact, Integrated Photoelectron Linacs

    NASA Astrophysics Data System (ADS)

    Yu, David

    2000-12-01

    The innovative compact high energy iniector which has been developed by DULY Research Inc., will have wide scientific industrial and medical applications. The new photoelectron injector integrates the photocathode directly into a multicell linear accelerator with no drift space between the injector and the linac. By focusing the beam with solenoid or permanent magnets, and producing high current with low emittance, extremely high brightness is achieved. In addition to providing a small footprint and improved beam quality in an integrated structure, the compact system considerably simplifies external subsystems required to operate the photoelectron linac, including rf power transport, beam focusing, vacuum and cooling. The photoelectron linac employs an innovative Plane-Wave-Transformer (PWT) design, which provides strong cell-to-cell coupling, relaxes manufacturing tolerance and facilitates the attachment of external ports to the compact structure with minimal field interference. DULY Research Inc. under the support of the DOE Small Business Innovation Research (SBIR) program, has developed, constructed and installed a 20-MeV, S-band compact electron source at UCLA. DULY Research is also presently engaged in the development of an X-band photoelectron linear accelerator in another SBIR project. The higher frequency structure when completed will be approximately three times smaller, and capable of a beam brightness ten times higher than the S-band structure.

  9. Ionospheric photoelectrons: Comparing Venus, Earth, Mars and Titan

    NASA Astrophysics Data System (ADS)

    Coates, A. J.; Tsang, S. M. E.; Wellbrock, A.; Frahm, R. A.; Winningham, J. D.; Barabash, S.; Lundin, R.; Young, D. T.; Crary, F. J.

    2011-08-01

    The sunlit portion of planetary ionospheres is sustained by photoionization. This was first confirmed using measurements and modelling at Earth, but recently the Mars Express, Venus Express and Cassini-Huygens missions have revealed the importance of this process at Mars, Venus and Titan, respectively. The primary neutral atmospheric constituents involved (O and CO 2 in the case of Venus and Mars, O and N 2 in the case of Earth and N 2 in the case of Titan) are ionized at each object by EUV solar photons. This process produces photoelectrons with particular spectral characteristics. The electron spectrometers on Venus Express and Mars Express (part of ASPERA-3 and 4, respectively) were designed with excellent energy resolution (Δ E/ E=8%) specifically in order to examine the photoelectron spectrum. In addition, the Cassini CAPS electron spectrometer at Saturn also has adequate resolution (Δ E/ E=16.7%) to study this population at Titan. At Earth, photoelectrons are well established by in situ measurements, and are even seen in the magnetosphere at up to 7 RE. At Mars, photoelectrons are seen in situ in the ionosphere, but also in the tail at distances out to the Mars Express apoapsis (˜3 RM). At both Venus and Titan, photoelectrons are seen in situ in the ionosphere and in the tail (at up to 1.45 RV and 6.8 RT, respectively). Here, we compare photoelectron measurements at Earth, Venus, Mars and Titan, and in particular show examples of their observation at remote locations from their production point in the dayside ionosphere. This process is found to be common between magnetized and unmagnetized objects. We discuss the role of photoelectrons as tracers of the magnetic connection to the dayside ionosphere, and their possible role in enhancing ion escape.

  10. 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.

  11. Photoionization and photoelectric loading of barium ion traps

    SciTech Connect

    Steele, A. V.; Churchill, L. R.; Griffin, P. F.; Chapman, M. S.

    2007-05-15

    Simple and effective techniques for loading barium ions into linear Paul traps are demonstrated. Two-step photoionization of neutral barium is achieved using a weak intercombination line (6s{sup 2} {sup 1}S{sub 0}{r_reversible}6s6p {sup 3}P{sub 1}, {lambda}=791 nm) followed by excitation above the ionization threshold using a nitrogen gas laser ({lambda}=337 nm). Isotopic selectivity is achieved by using a near Doppler-free geometry for excitation of the triplet 6s6p {sup 3}P{sub 1} state. Additionally, we report a particularly simple and efficient trap loading technique that employs an inexpensive uv epoxy curing lamp to generate photoelectrons.

  12. Photoionization dynamics of pure helium droplets: exciton formation vs autoionization

    NASA Astrophysics Data System (ADS)

    Kornilov, Oleg; Gessner, Oliver; Buennermann, Oliver; Wang, Chia; Leone, Steve; Neumark, Daniel

    2010-03-01

    ^4He droplets possess unique properties. In addition to fundamental quantum effects of superfluidity the droplets show ability to efficiently pick-up foreign atoms, molecules and complexes, which is used in a number of matrix isolation spectroscopies in energy domain. Complementary to these studies, novel time-domain experiments will be presented emphasizing dynamics of photoionization of pure helium droplets. The experiments follow up on a recent observation of ultraslow (E<1 meV) photoelectrons emitted from droplets upon ionization by synchrotron radiation. The dynamics of photoionization is studied by exciting droplets with a pulsed VUV radiation generated using the high-order harmonic generation technique. The droplets subsequently interact with an IR pulse, which probes transient electronic states before droplet autoionization. Femtosecond and picosecond relaxation dynamics and competition between droplet ionization and formation of a long-lived excited state are observed. Probe pulse leads to droplet ``re-excitation'' and production of even more ultraslow electrons. The results will be extended to doped droplets anticipating indirect dopant ionization dynamics.

  13. IONIS: Approximate atomic photoionization intensities

    NASA Astrophysics Data System (ADS)

    Heinäsmäki, Sami

    2012-02-01

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

  14. 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. Attosecond photoelectron microscopy of H2+

    NASA Astrophysics Data System (ADS)

    Hu, S. X.; Collins, L. A.; Schneider, B. I.

    2009-08-01

    We present a numerical study of the ultrafast ionization dynamics of H2+ exposed to attosecond extreme ultraviolet (xuv) pulses that goes beyond the Born-Openheimer approximation. The four-dimensional, time-dependent Schrödinger equation was solved using a generalization of the finite-element discrete-variable-representation/real-space-product technique used in our previous calculations to include the dynamical motion of the nuclei. This has enabled us to expose the target to any polarized light at arbitrary angles with respect to the molecular axis. Calculations have been performed at different angles and photon energies ( ℏω=50eV up to 630 eV) to investigate the energy and orientation dependence of the photoionization probability. A strong orientation dependence of the photoionization probability of H2+ was found at a photon energy of ℏω=50eV . At this energy, we found that the ionization probability is three times larger in the perpendicular polarization than in the parallel case. These observations are explained by the different geometric “cross sections” seen by the photoejected electron as it leaves the molecule. This ionization anisotropy vanishes at the higher-photon energy of ℏω≥170eV . When these higher-energy xuv pulses are polarized perpendicular to the internuclear axis, a “double-slit-like” interference pattern is observed. However, we find that the diffraction angle only approaches the classical formula ϕn=sin-1(nλe/R0) , where n is the diffraction order, λe is the released electron wavelength, and R0 is the internuclear distance, when nλe becomes less than 65% of R0 . These results illustrate the possibility of employing attosecond pulses to perform photoelectron microscopy of molecules.

  17. Photoionization Efficiencies of Five Polycyclic Aromatic Hydrocarbons.

    PubMed

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

    2017-06-15

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

  18. Photoionization Efficiencies of Five Polycyclic Aromatic Hydrocarbons

    DOE PAGES

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

    2017-05-18

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

  19. Photoelectronic Radiology Department

    NASA Astrophysics Data System (ADS)

    Capp, M. P.; Nudelman, Sol; Fisher, Donald; Ovitt, Theron W.; Pond, Gerald D.; Frost, Meryl M.; Roehrig, Hans; Seeger, Joachim; Oimette, Donald

    1981-11-01

    The University of Arizona Department of Radiology first considered establishing a photoelectronic radiology department in 1973. It seemed clear that the technology had progressed far enough for us to investigate the possibility of total film replacement.' Data from the space program in particular indicated at that time that sophisticated television images over 1000 x 1000 lines were approaching the detail seen on the traditional x-ray film. This technology has been known over many years of research and development as "photoelectronic imaging devices (PEID) ."14 However, at that time film replacement was out of the question. What was not out of the question was the consideration of using a subtraction technique, "digital video subtraction angiography." To this end, we, and independently the University of Wisconsin,314 proceeded to develop this technology.5'6 Our intravenous video subtraction images in patients started in our research laboratory in 1977 and in March of 1980 we opened a biplane special procedures room dedicated only to photoelectronic imaging (no film).7'8 Digital video subtraction angiography has been successful and is described in much greater detail in these Proceedings by other authors. Current efforts are under way toward total replacement of film. This is an immense problem, one that will require a much greater sophistication of computers, storage devices, system analysis, and cooperation from both the radiologist and the clinician.9'10 In a theoretical study we converted our 65,000 procedures-per-year department to complete photoelectronic imaging (no film) and estimated that we would save approximately five million dollars over ten years.15 Extrapolating this to the entire United States would result in a conservative estimate of saving one billion dollars per year. Not included in these mathematics are cost-effective savings of the physicians' time and effort.

  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. Emitter-site-selective photoelectron circular dichroism of trifluoromethyloxirane

    NASA Astrophysics Data System (ADS)

    Ilchen, M.; Hartmann, G.; Rupprecht, P.; Artemyev, A. N.; Coffee, R. N.; Li, Z.; Ohldag, H.; Ogasawara, H.; Osipov, T.; Ray, D.; Schmidt, Ph.; Wolf, T. J. A.; Ehresmann, A.; Moeller, S.; Knie, A.; Demekhin, Ph. V.

    2017-05-01

    The angle-resolved inner-shell photoionization of R-trifluoromethyloxirane, C3H3F3O , is studied experimentally and theoretically. Thereby, we investigate the photoelectron circular dichroism (PECD) for nearly symmetric O 1 s and F 1 s electronic orbitals, which are localized on different molecular sites. The respective dichroic β1 and angular distribution β2 parameters are measured at the photoelectron kinetic energies from 1 to 16 eV by using variably polarized synchrotron radiation and velocity map imaging spectroscopy. The present experimental results are in good agreement with the outcome of ab initio electronic structure calculations. We report a sizable chiral asymmetry β1 of up to about 9% for the K -shell photoionization of oxygen atom. For the individual fluorine atoms, the present calculations predict asymmetries of similar size. However, being averaged over all fluorine atoms, it drops down to about 2%, as also observed in the present experiment. Our study demonstrates a strong emitter and site sensitivity of PECD in the one-photon inner-shell ionization of this chiral molecule.

  2. Emitter-site-selective photoelectron circular dichroism of trifluoromethyloxirane

    DOE PAGES

    Ilchen, M.; Hartmann, G.; Rupprecht, P.; ...

    2017-05-30

    The angle-resolved inner-shell photoionization of R-trifluoromethyloxirane, C3H3F3O, is studied experimentally and theoretically. Thereby, we investigate the photoelectron circular dichroism (PECD) for nearly symmetric O 1s and F 1s electronic orbitals, which are localized on different molecular sites. The respective dichroic β1 and angular distribution β2 parameters are measured at the photoelectron kinetic energies from 1 to 16 eV by using variably polarized synchrotron radiation and velocity map imaging spectroscopy. The present experimental results are in good agreement with the outcome of ab initio electronic structure calculations. We report a sizable chiral asymmetry β1 of up to about 9% for themore » K -shell photoionization of oxygen atom. For the individual fluorine atoms, the present calculations predict asymmetries of similar size. However, being averaged over all fluorine atoms, it drops down to about 2%, as also observed in the present experiment. Our study demonstrates a strong emitter and site sensitivity of PECD in the one-photon inner-shell ionization of this chiral molecule.« less

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

    NASA Astrophysics Data System (ADS)

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

    2014-06-01

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

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

    SciTech Connect

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

    2014-08-21

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

  5. 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

  6. 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.

  7. 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.

  8. Elucidating the thermal decomposition of dimethyl methylphosphonate by vacuum ultraviolet (VUV) photoionization: pathways to the PO radical, a key species in flame-retardant mechanisms.

    PubMed

    Liang, Shuyu; Hemberger, Patrick; Neisius, N Matthias; Bodi, Andras; Grützmacher, Hansjörg; Levalois-Grützmacher, Joelle; Gaan, Sabyasachi

    2015-01-12

    The production of phosphoryl species (PO, PO2, HOPO) is believed to be of great importance for efficient flame-retardant action in the gas phase. We present a detailed investigation of the thermal decomposition of dimethyl methylphosphonate (DMMP) probed by vacuum ultraviolet (VUV) synchrotron radiation and imaging photoelectron photoion coincidence (iPEPICO) spectroscopy. This technique provides a snapshot of the thermolysis process and direct evidence of how the reactive phosphoryl species are generated during heat exposure. One of the key findings of this work is that only PO is formed in high concentration upon DMMP decomposition, whereas PO2 is absent. It can be concluded that the formation of PO2 needs an oxidative environment, which is typically the case in a real flame. Based on the identification of products such as methanol, formaldehyde, and PO, as well as the intermediates O=P-CH3, H2C=P-OH, and H2C=P(=O)H, supported by quantum chemical calculations, we were able to describe the predominant pathways that lead to active phosphoryl species during the thermal decomposition of DMMP. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. High-energy non-Franck-Condon vibrational excitation of CH4 by intramolecular photoelectron diffraction

    NASA Astrophysics Data System (ADS)

    Argenti, L.; Plésiat, E.; Kukk, E.; Ueda, K.; Decleva, P.; Martín, F.

    2012-11-01

    Distinct oscillations in vibrationally resolved cross section ratios for the photoionization of CH4 from the C 1s orbital at photon energies as high as 1keV are predicted. The oscillations are attributed to the different relative vibrational excitation due to the scattering of the photoelectron by the peripheral hydrogen atoms. The latter effect is also responsible for the well known EXAFS oscillations in the integrated photoelectron spectrum. The calculations are performed with an ab-initio DFT method [1], as well as with a single-particle semi-analytical model, which incorporate both the effect of the nuclear recoil and of the Coulomb corrections.

  10. Ionospheric photoelectrons: comparing Venus, Earth, Mars and Titan

    NASA Astrophysics Data System (ADS)

    Coates, Andrew; Tsang, Sharon; Wellbrock, Anne; Frahm, Rudy; Winningham, David; Barabash, Stas; Lundin, Rickard; Young, David; Crary, Frank

    2010-05-01

    The sunlit portion of planetary ionospheres is sustained by photoionization. This was first confirmed using measurements and modelling at Earth, but recently the Mars Express, Venus Express and Cassini-Huygens missions have revealed the importance of this process at Mars, Venus and Titan respectively. The primary neutral atmospheric constituents (CO2 in the case of Venus and Mars, and N2 in the case of Earth and Titan) are ionized at each object by EUV solar photons. This process produces photoelectrons with particular spectral characteristics. The electron spectrometers on Venus Express and Mars Express (part of ASPERA-3 and 4 respectively) were designed with excellent energy resolution (ΔE/E=8%) specifically in order to examine the photoelectron spectrum. In addition, the CAPS electron spectrometer at Saturn also has adequate resolution (ΔE/E=16.7%) to study this population at Titan. At Earth, photoelectrons are well established by in-situ measurements, and are even seen in the magnetosphere at up to 7 RE. At Mars, photoelectrons are seen in situ in the ionosphere but also in the tail at distances out to the Mars Express apoapsis (~3RM). At both Venus and Titan, photoelectrons are seen in situ in the ionosphere and in the tail (at up to 1.45 RV and 6.8 RT respectively). Here, we compare photoelectron measurements at Earth, Venus, Mars and Titan. We discuss their role as a tracer of the magnetic connection to the dayside ionosphere, and their possible role in enhancing ion escape.

  11. The study of state-selected ion-molecule reactions using the vacuum ultraviolet pulsed field ionization-photoion technique.

    PubMed

    Dressler, Rainer A; Chiu, Y; Levandier, D J; Tang, X N; Hou, Y; Chang, C; Houchins, C; Xu, H; Ng, Cheuk-Yiu

    2006-10-07

    This paper presents the methodology to generate beams of ions in single quantum states for bimolecular ion-molecule reaction dynamics studies using pulsed field ionization (PFI) of atoms or molecules in high-n Rydberg states produced by vacuum ultraviolet (VUV) synchrotron or laser photoexcitation. Employing the pseudocontinuum high-resolution VUV synchrotron radiation at the Advanced Light Source as the photoionization source, PFI photoions (PFI-PIs) in selected rovibrational states have been generated for ion-molecule reaction studies using a fast-ion gate to pass the PFI-PIs at a fixed delay with respect to the detection of the PFI photoelectrons (PFI-PEs). The fast ion gate provided by a novel interleaved comb wire gate lens is the key for achieving the optimal signal-to-noise ratio in state-selected ion-molecule collision studies using the VUV synchrotron based PFI-PE secondary ion coincidence (PFI-PESICO) method. The most recent development of the VUV laser PFI-PI scheme for state-selected ion-molecule collision studies is also described. Absolute integral cross sections for state-selected H2+ ions ranging from v+ = 0 to 17 in collisions with Ar, Ne, and He at controlled translational energies have been obtained by employing the VUV synchrotron based PFI-PESICO scheme. The comparison between PFI-PESICO cross sections for the H2+(HD+)+Ne and H2+(HD+)+He proton-transfer reactions and theoretical cross sections based on quasiclassical trajectory (QCT) calculations and three-dimensional quantum scattering calculations performed on the most recently available ab initio potential energy surfaces is highlighted. In both reaction systems, quantum scattering resonances enhance the integral cross sections significantly above QCT predictions at low translational and vibrational energies. At higher energies, the agreement between experiment and quasiclassical theory is very good. The profile and magnitude of the kinetic energy dependence of the absolute integral cross

  12. 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.

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

    NASA Astrophysics Data System (ADS)

    Bowen, Kyle Patrick

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

  14. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2010-03-01

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

  16. Double photoionization of halogenated benzene

    SciTech Connect

    AlKhaldi, Mashaal Q.; Wehlitz, Ralf

    2016-01-28

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

  17. Photoionization of ClII

    NASA Astrophysics Data System (ADS)

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

    2014-05-01

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

  18. Indirect double photoionization of water

    NASA Astrophysics Data System (ADS)

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

    2011-05-01

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

  19. 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.

  20. 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.

  1. Vector potential photoelectron microscopy.

    PubMed

    Browning, R

    2011-10-01

    A new class of electron microscope has been developed for the chemical microanalysis of a wide range of real world samples using photoelectron spectroscopy. Highly structured, three-dimensional samples, such as fiber mats and fracture surfaces can be imaged, as well as insulators and magnetic materials. The new microscope uses the vector potential field from a solenoid magnet as a spatial reference for imaging. A prototype instrument has demonstrated imaging of uncoated silk, magnetic steel wool, and micron-sized single strand tungsten wires.

  2. 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)

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

    NASA Astrophysics Data System (ADS)

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

    2012-02-01

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

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

    NASA Astrophysics Data System (ADS)

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

    1997-12-01

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

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

    DTIC Science & Technology

    1982-07-19

    following pages. -4- PAPERS 1. B. E. Cole, D. L. Ederer, R. Stockbauer, K. Codling, A. C. Parr, J. B. est, E. D. Poliakoff , and J. L. Dehmer... Poliakoff , P. M. Dehmer, J. L. Dehmer, and R. L. Stockbauer, "The Photoelectron Spectrum of Xe 3 by the Photoelectron-Photoon Coincidence Technique," J... Poliakoff , P. M. Dehmer, J. L. Dehmer, and R. Smok.b,,uer. "Photo- electron-Photolon Coincidence Spectroscopy of Gas-Phdse CluerL," 1. Gher. Phys. 76, 5214

  6. 4d Photoionization of Free Singly Charged Xenon Ions

    NASA Astrophysics Data System (ADS)

    Gottwald, A.; Gerth, Ch.; Richter, M.

    1999-03-01

    Electron spectroscopy in direct 4d photoionization of free Xe+ ions has been realized for the first time, applying various timing and coincidence techniques to suppress and to monitor on line the strong fluctuating background. The ionization energies of 4d5/2 and 4d3/2 electrons of Xe+\\(5p5 2P3/2\\) and Xe+\\(5p5 2P1/2\\) were determined and compared to calculated RHF(CI) values and to corresponding results of neutral Xe\\(5p6 1S0\\) atoms to study the influence of the outer-shell electron occupation on the 4d-1 inner-shell process.

  7. An experimental Method to Determine Photoelectron Partial Wave Probabilities and the Implications for Quantum Mechanically Complete Experiments

    NASA Astrophysics Data System (ADS)

    Yenen, Orhan

    2003-05-01

    Recent trends in AMO physics is to move from being a passive observer to an active controller of the outcome of quantum phenomena. Full controls of quantum processes require complete information about the quantum system; experiments which measure all the information allowed by quantum mechanics are called "Quantum Mechanically Complete Experiments". For example, when an isolated atom is photoionized, conservation laws limit the allowed partial waves of the photoelectron to a maximum of three. A quantum mechanically complete photoionization experiment then will have to determine all three partial wave probabilities and the two independent phases between the partial waves as a function of ionizing photon energy. From these five parameters all the quantities quantum mechanics allows one to measure can be determined for the "Residual Ion + Photoelectron" system. We have developed experimental methods [1, 2] to determine all three partial wave probabilities of photoelectrons when the residual ion is left in an excited state. Experimentally, Ar atoms are photoionized by circularly polarized synchrotron radiation produced by a unique VUV (vacuum ultraviolet) phase retarder we have installed at the Advanced Light Source (ALS) in Berkeley, CA. We measure the linear and circular polarization of the fine-structure-resolved fluorescent photons from the excited residual ions at specific directions. From the measurements one obtains the relativistic partial wave probabilities of the photoelectron. Our measurements highlight the significance of multielectron processes in photoionization dynamics and provide stringent tests of theory. The results indicate significant spin-dependent relativistic interactions during photoionization. [1] O. Yenen et al., Phys. Rev. Lett. 86, 979 (2001). [2] K. W. McLaughlin et al., Phys. Rev. Lett. 88, 123003 (2002).

  8. Alignment of photoions far from threshold

    NASA Astrophysics Data System (ADS)

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

    1994-09-01

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

  9. Photoelectron pumped phosphors

    NASA Astrophysics Data System (ADS)

    1989-07-01

    The investigation of cathodophosphors was undertaken in connection with the development of optical devices for the detection of long wavelength photons in which the initial photon-to-electron detection is performed by an optical diode. Then the photoelectrons being accelerated by the electric field penetrate into a phosphor screen and the screen produces multiple photons which are detected by a (close coupled) photomultiplier. The results are presented of a comprehensive analysis and systematization of the data relevant to the fast and very fast commercially available phosphors and developmental works on improved materials and processes in the field of phosphors, especially cathodophosphors. The investigation included analysis of II-VI phosphors, alkaline-earth chalcogenides, silicates, garnets, halides, and some ternary compounds with diamond-like crystal structure. The investigation included, also, analysis of data regarding the activators and coactivators as well as mixtures of phosphors with optically transparent conductive powders for the low energy electron cathodoluminescence.

  10. 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.

  11. Analysis of 3d photoionization and subsequent Auger decay of atomic germanium

    SciTech Connect

    Jaenkaelae, K.; Anin, D.; Huttula, S.-M.; Heinaesmaeki, S.; Huttula, M.; Urpelainen, S.

    2011-11-15

    Experimental and theoretical study of the 3d photoionization and subsequent Auger decay of initially neutral atomic germanium is presented. The features of the high-resolution photoelectron and Auger electron spectra are interpreted with the aid of multiconfiguration calculations. The binding energies and relative cross sections of the 3d ionized fine-structure states of Ge are given. The complete M{sub 4,5}NN Auger electron spectrum to doubly ionized final states of the Ge ion is interpreted and discussed.

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

    DTIC Science & Technology

    1981-07-06

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

  13. 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.

  14. 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.

  15. Double Photoionization of Atomic Beryllium

    NASA Astrophysics Data System (ADS)

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

    2010-03-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2001-08-01

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

  17. 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.

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

    SciTech Connect

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

    2016-03-30

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

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

    DOE PAGES

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

    2016-03-30

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

  20. 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

  1. Theory of attosecond delays in molecular photoionization

    NASA Astrophysics Data System (ADS)

    Baykusheva, Denitsa; Wörner, Hans Jakob

    2017-03-01

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

  2. Competition between ultrafast relaxation and photoionization in excited prefluorescent states of tryptophan and indole

    NASA Astrophysics Data System (ADS)

    Sherin, P. S.; Snytnikova, O. A.; Tsentalovich, Yu. P.; Sagdeev, R. Z.

    2006-10-01

    The quantum yield of photoionization of TrpH and IndH from the nonrelaxed prefluorescent state S* increases with the temperature decrease. This effect is attributed to the competition between temperature independent ionization and ultrafast thermal relaxation S*→S1. The rate constant of the relaxation does not depend on the solvent and on the presence of the amino acid side chain: the temperature dependences of photoionization quantum yield, obtained for TrpH and IndH in different solvents, practically coincide. The activation energy for the relaxation rate constant Er≈4.5kJ/mol probably corresponds to intramolecular process or to the formation of the vibronically excited transient complex between photoexcited molecule and solvent molecules.

  3. EUV optics in photoionization experiments

    NASA Astrophysics Data System (ADS)

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

    2013-05-01

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

  4. 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

    2014-06-06

    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.

  5. Grafting of Ring-Opened Cyclopropylamine Thin Films on Silicon (100) Hydride via UV Photoionization.

    PubMed

    Tung, J; Ching, J Y; Ng, Y M; Tew, L S; Khung, Y L

    2017-08-31

    The grafting of cyclopropylamine onto a silicon (100) hydride (Si-H) surface via a ring-opening mechanism using UV photoionization is described here. In brief, radicals generated from the Si-H surface upon UV irradiation were found to behave in classical hydrogen abstraction theory manner by which the distal amine group was first hydrogen abstracted and the radical propagated down to the cyclopropane moiety. This subsequently liberated the strained bonds of the cyclopropane group and initiated the surface grafting process, producing a thin film approximately 10-15 nm in height. Contact angle measurements also showed that such photoionization irradiation had yielded an extremely hydrophilic surface (∼21.3°) and X-ray photoelectron spectroscopy also confirmed the coupling was through the Si-C linkage. However, when the surface underwent high-temperature hydrosilylation (>160 °C), the reaction proceeded predominantly through the nucleophilic NH2 group to form a Si-N linkage to the surface. This rendered the surface hydrophobic and hence suggested that the Si-H homolysis model may not be the main process. To the best of our knowledge, this was the first attempt reported in the literature to use photoionization to directly graft cyclopropylamine onto a silicon surface and in due course generate a highly rich NH-terminated surface that was found to be highly bioactive in promoting cell viability on the basis of 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide studies.

  6. Photo-ionization rate coefficients for the rare gases

    NASA Astrophysics Data System (ADS)

    Pang, Xuexia

    2005-01-01

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

  7. Photoelectron angular distributions from two-photon ionizations of atoms

    NASA Astrophysics Data System (ADS)

    Haber, Louis Hamilton

    Photoelectron angular distributions provide detailed information about interferences between different quantum pathways of photoionization. Measurements of photoelectron energies and angular distributions from two-color two-photon ionizations of atoms using ultrashort pulses of extreme ultraviolet and optical light are performed using a novel, homebuilt experimental instrument. The setup is composed of an amplified femtosecond laser system, a high-order harmonic generation source, and an interaction region with photoelectron velocity map imaging The experimental temporal resolution is determined to be approximately 100 fs. Two different types of two-photon ionizations are investigated. Photoelectron angular distributions from resonant two-photon ionizations of helium are measured using the 15th high-order harmonic to excite from the ground state to either the 1s3p 1P1 state at 23.1 eV or to the 1s4p 1 P1 state at 23.7 eV and either 800, 400, or 267 nm to ionize. The anisotropy parameters allow for the determination of the energy-dependent ratios of radial dipole matrix elements and the phase shift differences between the S and D partial waves. Using available total cross section measurements, the absolute partial cross sections of the 1s3p1P 1 state are obtained, providing the complete information on photoionization. The experimental results are in excellent agreement with theoretical predictions using the one-electron model. Additional experiments are aimed at studying atomic free-free transitions. Two-color two-photon above threshold ionizations of helium and argon are investigated using selected high-order harmonics and perturbative infrared dressing fields. The measured anisotropy parameters and cross section ratios of the positive and negative above threshold ionization sidebands are compared to theoretical predictions using second-order perturbation theory and the soft-photon approximation. In general, deviations between the experimental results and the

  8. 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.

  9. Double photoionization of hydrocarbons and aromatic molecules

    NASA Astrophysics Data System (ADS)

    Wehlitz, R.

    2016-11-01

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

  10. Photodissociation and photoionization of organosulfur radicals

    SciTech Connect

    Hsu, Chia-Wei

    1994-05-27

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

  11. Monitoring non-adiabatic dynamics in CS2 with time- and energy-resolved photoelectron spectra of wavepackets

    NASA Astrophysics Data System (ADS)

    Wang, Kwanghsi; McKoy, Vincent; Hockett, Paul; Stolow, Albert; Schuurman, Michael S.

    2017-09-01

    We report results from a novel fully ab initio method for simulating the time-resolved photoelectron angular distributions around conical intersections in CS2. The technique employs wavepacket densities obtained with the multiple spawning method in conjunction with geometry- and energy-dependent photoionization matrix elements. The robust agreement of the calculated molecular-frame photoelectron angular distributions with measured values for CS2 demonstrates that this approach can successfully illuminate, and disentangle, the underlying coupled nuclear and electronic dynamics around conical intersections in polyatomic molecules.

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

    NASA Astrophysics Data System (ADS)

    Matsuoka, Takahide; Takatsuka, Kazuo

    2017-04-01

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

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

    PubMed

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

    2006-02-21

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

  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. Absolute partial photoionization cross sections of ozone.

    SciTech Connect

    Berkowitz, J.; Chemistry

    2008-04-01

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

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

    PubMed

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

    2010-05-07

    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 S(2) and S(1) states in pyrazine. The simulations reveal that, parallel to the S(2)-->S(1) internal conversion, a change in the dominant ionization process (S(2)-->D(1) versus S(1)-->D(0)) 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.

  17. 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.

  18. Exploring ultrafast dynamics of pyrazine by time-resolved photoelectron imaging.

    PubMed

    Tomasello, Gaia; Humeniuk, Alexander; Mitrić, Roland

    2014-09-18

    We present the simulation of time-resolved photoelectron imaging spectra of pyrazine in the gas phase. The approach we have adopted is based on the combination of the ab initio nonadiabatic molecular dynamics "on the fly" with an approximate treatment of the photoionization process using Dyson orbitals and Coulomb functions to describe the bound and ionized states of the photoelectron. The method has been implemented (Humeniuk, A.; et al. J. Chem. Phys 2013, 139, 134104) in the framework of the time-dependent density functional theory and has been applied here to interrogate the ultrafast internal conversion between the S2 and S1 states in pyrazine. Conventional time-resolved photoelectron spectra without angular resolution fail to locate the S2 → S1 internal conversion, because the ionization potentials relevant for the photoionization channels S2 → D1 (π(-1)) and S1 → D0 (n(-1)) are almost identical. Introducing the angular resolution in the photoelectron spectra reveals evidence of such ultrafast internal conversion and provides a more detailed picture of the overall dynamics. The simulated time- and energy-dependent anisotropy map obtained within the Dyson/time-dependent density functional theory approach is in good agreement with its experimental counterpart provided by Horio et al. (Horio, T.; et al. J. Am. Chem. Soc. 2009, 131, 10932). Our theoretical approach represents a general tool for mapping the time- and angle-resolved photoelectron spectra in complex systems and thus can be used to investigate the ultrafast relaxation processes occurring in isolated molecules.

  19. 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.

  20. Photoelectron spectroscopy of a series of acetate and propionate esters

    NASA Astrophysics Data System (ADS)

    Śmiałek, Małgorzata A.; Guthmuller, Julien; MacDonald, Michael A.; Zuin, Lucia; Delwiche, Jacques; Hubin-Franskin, Marie-Jeanne; Lesniewski, Tadeusz; Mason, Nigel J.; Limão-Vieira, Paulo

    2017-10-01

    The electronic state and photoionization spectroscopy of a series of acetate esters: methyl acetate, isopropyl acetate, butyl acetate and pentyl acetate as well as two propionates: methyl propionate and ethyl propionate, have been determined using vacuum-ultraviolet photoelectron spectroscopy. These experimental investigations are complemented by ab initio calculations. The measured first adiabatic and vertical ionization energies were determined as: 10.21 and 10.45 eV for methyl acetate, 9.99 and 10.22 eV for isopropyl acetate, 10.07 and 10.26 eV for butyl acetate, 10.01 and 10.22 eV for pentyl acetate, 10.16 and 10.36 eV for methyl propionate and 9.99 and 10.18 eV for ethyl propionate. For the four smaller esters vibrational transitions were calculated and compared with those identified in the photoelectron spectrum, revealing the most distinctive ones to be a Csbnd O stretch combined with a Cdbnd O stretch. The ionization energies of methyl and ethyl esters as well as for a series of formates and acetates were compared showing a clear dependence of the value of the ionization energy on the size of the molecule with very little influence of its conformation.

  1. Electronically forbidden (5σu-->kσu) photoionization of CS2: Mode-specific electronic-vibrational coupling

    NASA Astrophysics Data System (ADS)

    Rathbone, G. J.; Poliakoff, E. D.; Bozek, John D.; Lucchese, R. R.

    2005-02-01

    Vibrationally resolved photoelectron spectroscopy of the CS2+(BΣu +2) state is used to show how nontotally symmetric vibrations "activate" a forbidden electronic transition in the photoionization continuum, specifically, a 5σu→kσu shape resonance, that would be inaccessible in the absence of a symmetry breaking vibration. This electronic channel is forbidden owing to inversion symmetry selection rules, but it can be accessed when a nonsymmetric vibration is excited, such as bending or antisymmetric stretching. Photoelectron spectra are acquired for photon energies 17⩽hν⩽72eV, and it is observed that the forbidden vibrational transitions are selectively enhanced in the region of a symmetry-forbidden continuum shape resonance centered at hν ≈42eV. Schwinger variational calculations are performed to analyze the data, and the theoretical analysis demonstrates that the observed forbidden transitions are due to photoelectron-mediated vibronic coupling, rather than interchannel Herzberg-Teller mixing. We observe and explain the counterintuitive result that some vibrational branching ratios vary strongly with energy in the region of the resonance, even though the resonance position and width are not appreciably influenced by geometry changes that correspond to the affected vibrations. In addition, we find that another resonant channel, 5σu→kπg, influences the symmetric stretch branching ratio. All of the observed effects can be understood within the framework of the Chase adiabatic approximation, i.e., the Born-Oppenheimer approximation applied to photoionization.

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

    NASA Astrophysics Data System (ADS)

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

    2009-04-01

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

  3. Photoelectron detection from transient species in organic semiconducting thin films by dual laser pulse irradiation

    NASA Astrophysics Data System (ADS)

    Hosokai, Takuya; Matsuzaki, Hiroyuki; Furube, Akihiro; Nakamura, Ken

    2017-02-01

    An Nd3+:YAG pulsed laser was employed as a light source for two-photon photoemission from organic semiconducting thin films in low vacuum and air. Photoionization by the two-photon process was confirmed in both the environments by measuring photoemission current. By constructing a pump-probe system, photoemissions from transient species formed by the pump light irradiation were detected by probe light irradiation as a result of a linear increase in the photocurrent with the pump power via a one-photon process. Thus, we propose a novel method called two-photon photoelectron yield spectroscopy to determine the excited-state energy levels in ambient environments.

  4. Investigation of low-Z Coster-Kronig transitions by means of Auger and photoelectron spectroscopy

    NASA Technical Reports Server (NTRS)

    Yin, L. I.; Tsang, T.; Adler, I.

    1972-01-01

    Experimental intensity ratios of Auger transitions for Co, Ni, Cu, and Zn as well as the relative L sub 2 and L sub 3 level widths of Cu and Zn, derived from their photoelectron spectra, are presented. Evidence is presented that a great deal of vacancy reorganization took place following photoionization and prior to Auger emission. These reorganizations are assumed to be due to Coster-Kronig transitions f sub 23. These results are compared with theoretical calculations and agree with predicted discontinuity at Z = 30 where f sub 23 transitions become energetically impossible.

  5. Probing molecular frame photoelectron angular distributions via high-order harmonic generation from aligned molecules

    NASA Astrophysics Data System (ADS)

    Lin, C. D.; Jin, Cheng; Le, Anh-Thu; Lucchese, R. R.

    2012-10-01

    We analyse the theory of single photoionization (PI) and high-order harmonic generation (HHG) by intense lasers from aligned molecules. We show that molecular-frame photoelectron angular distributions can be extracted from these measurements. We also show that, under favourable conditions, the phase of PI transition dipole matrix elements can be extracted from the HHG spectra. Furthermore, by varying the polarization axis of the HHG generating laser with respect to the polarization axis of the aligning laser, it is possible to extract angle-dependent tunnelling ionization rates for different subshells of the molecules.

  6. Photoelectron circular dichroism of isopropanolamine

    NASA Astrophysics Data System (ADS)

    Catone, D.; Turchini, S.; Contini, G.; Prosperi, T.; Stener, M.; Decleva, P.; Zema, N.

    2017-01-01

    Spectroscopies based on circular polarized light are sensitive to the electronic and structural properties of chiral molecules. Photoelectron circular dichroism (PECD) is a powerful technique that combines the chiral sensitivity of the circular polarized light and the electronic information obtained by photoelectron spectroscopy. An experimental and theoretical PECD study of the outer valence and C 1s core states of 1-amino-2-propanol in the gas phase is presented. The experimental dichroic dispersions in the photoelectron kinetic energy are compared with theoretical calculations employing a multicentric basis set of B-spline functions and a Kohn-Sham Hamiltonian. In order to understand analogies and differences in the dichroism of structural isomers bearing the same functional groups, a comparison with previous PECD study of valence band of 2-amino-1-propanol is carried out.

  7. 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.

  8. 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.

  9. 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.

  10. Photoelectron backscattering in vacuum phototubes

    NASA Astrophysics Data System (ADS)

    Lubsandorzhiev, B. K.; Vasiliev, R. V.; Vyatchin, Y. E.; Shaibonov, B. A. J.

    2006-11-01

    In this article we describe results of studies of a photoelectron backscattering effect in vacuum phototubes: classical photomultipliers (PMT) and hybrid phototubes (PH). Late pulses occurring in PMTs are attributed to the photoelectron backscattering and distinguished from pulses due to an anode glow effect. The late pulses are measured in a number of PMTs and HPs with various photocathode sizes covering 1 50 cm range and different types of the first dynode materials and construction designs. It is shown that the late pulses are a generic feature of all vacuum photodetectors—PMTs and PHs—and they do not deteriorate dramatically amplitude and timing responses of vacuum phototubes.

  11. Time-dependent Cooling in Photoionized Plasma

    NASA Astrophysics Data System (ADS)

    Gnat, Orly

    2017-02-01

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

  12. Photoionization of P+: Experiment and theory

    NASA Astrophysics Data System (ADS)

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

    2017-01-01

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

  13. Photoionization of atomic hydrogen in electric field

    SciTech Connect

    Gorlov, Timofey V; Danilov, Viatcheslav V

    2010-01-01

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

  14. Isomer-dependent fragmentation dynamics of inner-shell photoionized difluoroiodobenzene

    DOE PAGES

    Ablikim, Utuq; Bomme, Cédric; Savelyev, Evgeny; ...

    2017-05-11

    The fragmentation dynamics of 2,6- and 3,5-difluoroiodobenzene after iodine 4d inner-shell photoionization with soft X-rays are studied using coincident electron and ion momentum imaging. By analyzing the momentum correlation between iodine and fluorine cations in three-fold ion coincidence events, we can distinguish the two isomers experimentally. Classical Coulomb explosion simulations are in overall agreement with the experimentally determined fragment ion kinetic energies and momentum correlations and point toward different fragmentation mechanisms and time scales. Finally, while most three-body fragmentation channels show clear evidence for sequential fragmentation on a time scale larger than the rotational period of the fragments, the breakupmore » into iodine and fluorine cations and a third charged co-fragment appears to occur within several hundred femtoseconds.« less

  15. Neon photoionized plasma experiment at Z

    NASA Astrophysics Data System (ADS)

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

    2016-10-01

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

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

    PubMed

    Suzuki, Yoshi-Ichi; Suzuki, Toshinori

    2012-11-21

    In a previous study [T. Horio, T. Fuji, Y.-I. Suzuki, and T. Suzuki, J. Am. Chem. Soc. 131, 10392 (2009)], we demonstrated that the time-energy map of photoelectron angular anisotropy enables unambiguous identification of ultrafast S(2)(ππ*)-S(1)(nπ*) internal conversion in pyrazine. A notable characteristic of this map is that the forbidden ionization process of D(0)(n(-1)) ← S(2)(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 S(0) equilibrium geometry reproduce the observed anisotropy parameters for D(0) ← S(2) and D(0) ← S(1) ionizations, respectively. On the other hand, they do not reproduce the small difference in the photoelectron anisotropy parameters for the D(1)(π(-1)) ← S(2) and D(0) ← S(1) 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 ka(g) shape resonance and that the difference between their photoelectron anisotropy parameters originates from the difference in the molecular geometry in D(1) ← S(2) and D(0) ← S(1).

  17. 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.

  18. Calculation of photoionization differential cross sections using complex Gauss-type orbitals.

    PubMed

    Matsuzaki, Rei; Yabushita, Satoshi

    2017-09-05

    Accurate theoretical calculation of photoelectron angular distributions for general molecules is becoming an important tool to image various chemical reactions in real time. We show in this article that not only photoionization total cross sections but also photoelectron angular distributions can be accurately calculated using complex Gauss-type orbital (cGTO) basis functions. Our method can be easily combined with existing quantum chemistry techniques including electron correlation effects, and applied to various molecules. The so-called two-potential formula is applied to represent the transition dipole moment from an initial bound state to a final continuum state in the molecular coordinate frame. The two required continuum functions, the zeroth-order final continuum state and the first-order wave function induced by the photon field, have been variationally obtained using the complex basis function method with a mixture of appropriate cGTOs and conventional real Gauss-type orbitals (GTOs) to represent the continuum orbitals as well as the remaining bound orbitals. The complex orbital exponents of the cGTOs are optimized by fitting to the outgoing Coulomb functions. The efficiency of the current method is demonstrated through the calculations of the asymmetry parameters and molecular-frame photoelectron angular distributions of H2+ and H2 . In the calculations of H2 , the static exchange and random phase approximations are employed, and the dependence of the results on the basis functions is discussed. © 2017 Wiley Periodicals, Inc. © 2017 Wiley Periodicals, Inc.

  19. Photoelectrons and solar ionizing radiation at Mars: Predictions versus MAVEN observations

    NASA Astrophysics Data System (ADS)

    Peterson, W. K.; Thiemann, E. M. B.; Eparvier, Francis G.; Andersson, Laila; Fowler, C. M.; Larson, Davin; Mitchell, Dave; Mazelle, Christian; Fontenla, Juan; Evans, J. Scott; Xu, Shaosui; Liemohn, Mike; Bougher, Stephen; Sakai, Shotaro; Cravens, T. E.; Elrod, M. K.; Benna, M.; Mahaffy, P.; Jakosky, Bruce

    2016-09-01

    Understanding the evolution of the Martian atmosphere requires knowledge of processes transforming solar irradiance into thermal energy well enough to model them accurately. Here we compare Martian photoelectron energy spectra measured at periapsis by Mars Atmosphere and Volatile Evolution MissioN (MAVEN) with calculations made using three photoelectron production codes and three solar irradiance models as well as modeled and measured CO2 densities. We restricted our comparisons to regions where the contribution from solar wind electrons and ions were negligible. The two intervals examined on 19 October 2014 have different observed incident solar irradiance spectra. In spite of the differences in photoionization cross sections and irradiance spectra used, we find the agreement between models to be within the combined uncertainties associated with the observations from the MAVEN neutral density, electron flux, and solar irradiance instruments.

  20. Atomic ionization by intense laser pulses of short duration: Photoelectron energy and angular distributions

    SciTech Connect

    Dondera, M.

    2010-11-15

    We introduce an adequate integral representation of the wave function in the asymptotic region, valid for the stage postinteraction between a one-electron atom and a laser pulse of short duration, as a superposition of divergent radial spherical waves. Starting with this representation, we derive analytic expressions for the energy and angular distributions of the photoelectrons and we show their connection with expressions used before in the literature. Using our results, we propose a method to extract the photoelectron distributions from the time dependence of the wave function at large distances. Numerical results illustrating the method are presented for the photoionization of hydrogenlike atoms from the ground state and several excited states by extreme ultraviolet pulses with a central wavelength of 13.3 nm and several intensities around the value I{sub 0}{approx_equal}3.51x10{sup 16} W/cm{sup 2}.

  1. Unified ab initio treatment of attosecond photoionization and Compton scattering

    NASA Astrophysics Data System (ADS)

    Yudin, G. L.; Bondar, D. I.; Patchkovskii, S.; Corkum, P. B.; Bandrauk, A. D.

    2009-10-01

    We present a new theoretical approach to attosecond laser-assisted photo- and Compton ionization. Attosecond x-ray absorption and scattering are described by \\hat{\\mathscr{S}}^{(1,2)} -matrices, which are coherent superpositions of 'monochromatic' \\skew{3}\\hat{S}^{(1,2)} -matrices in a laser-modified Furry representation. Besides refining the existing theory of the soft x-ray photoelectron attosecond streak camera and spectral phase interferometry (ASC and ASPI), we formulate a theory of hard x-ray photoelectron and Compton ASC and ASPI. The resulting scheme has a simple structure and leads to closed-form expressions for ionization amplitudes. We investigate Compton electron interference in the separable Coulomb-Volkov continuum with both Coulomb and laser fields treated non-perturbatively. We find that at laser-field intensities below 1013 Wcm-2 normalized Compton lines almost coincide with the lines obtained in the laser-free regime. At higher intensities, attosecond interferences survive integration over electron momenta, and feature prominently in the Compton lines themselves. We define a regime where the electron ground-state density can be measured with controllable accuracy in an attosecond time interval. The new theory provides a firm basis for extracting photo- and Compton electron phases and atomic and molecular wavefunctions from experimental data.

  2. Relaxation Dynamics in Photoexcited Chiral Molecules Studied by Time-Resolved Photoelectron Circular Dichroism: Toward Chiral Femtochemistry

    PubMed Central

    2016-01-01

    Unravelling the main initial dynamics responsible for chiral recognition is a key step in the understanding of many biological processes. However, this challenging task requires a sensitive enantiospecific probe to investigate molecular dynamics on their natural femtosecond time scale. Here we show that, in the gas phase, the ultrafast relaxation dynamics of photoexcited chiral molecules can be tracked by recording time-resolved photoelectron circular dichroism (TR-PECD) resulting from the photoionization by a circularly polarized probe pulse. A large forward–backward asymmetry along the probe propagation axis is observed in the photoelectron angular distribution. Its evolution with pump–probe delay reveals ultrafast dynamics that are inaccessible in the angle-integrated photoelectron spectrum or via the usual electron emission anisotropy parameter (β). PECD, which originates from the electron scattering in the chiral molecular potential, appears as a new sensitive observable for ultrafast molecular dynamics in chiral systems. PMID:27786493

  3. 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.

  4. 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.

  5. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2017-06-01

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

  7. Photoelectron spectroscopy of molecular clusters

    NASA Astrophysics Data System (ADS)

    Zhang, Xu; Pitts, Jonathan; Zheng, Chaowen; Knee, Joseph L.

    1995-09-01

    High resolution photoelectron spectroscopy is applied to the study of molecular clusters. The primary species studied are fluorene-Arn complexes. Spectroscopy of the neutral S1 state has been performed on clusters as large as n equals 30. In order to study the photoelectron spectra of the clusters size selectively mass analyzed threshold ionization (MATI) is used which is a mass resolved version of the ZEKE technique. MATI spectroscopy has been applied to clusters up to n equals 5. The spectral shifts in the S1 origin and ion threshold are used as a measure of the relative stability of the different clusters. Using previous experimental and theoretical work on related clusters the structures of the clusters are inferred from the observed spectral shifts. In some cases multiple conformations of a particular cluster size are identified.

  8. Digital coincidence counting - initial results

    NASA Astrophysics Data System (ADS)

    Butcher, K. S. A.; Watt, G. C.; Alexiev, D.; van der Gaast, H.; Davies, J.; Mo, Li; Wyllie, H. A.; Keightley, J. D.; Smith, D.; Woods, M. J.

    2000-08-01

    Digital Coincidence Counting (DCC) is a new technique in radiation metrology, based on the older method of analogue coincidence counting. It has been developed by the Australian Nuclear Science and Technology Organisation (ANSTO), in collaboration with the National Physical Laboratory (NPL) of the United Kingdom, as a faster more reliable means of determining the activity of ionising radiation samples. The technique employs a dual channel analogue-to-digital converter acquisition system for collecting pulse information from a 4π beta detector and an NaI(Tl) gamma detector. The digitised pulse information is stored on a high-speed hard disk and timing information for both channels is also stored. The data may subsequently be recalled and analysed using software-based algorithms. In this letter we describe some recent results obtained with the new acquistion hardware being tested at ANSTO. The system is fully operational and is now in routine use. Results for 60Co and 22Na radiation activity calibrations are presented, initial results with 153Sm are also briefly mentioned.

  9. Observation of Interference between Two Distinct Autoionizing States in Dissociative Photoionization of H2

    NASA Astrophysics Data System (ADS)

    Reddish, T. J.; Padmanabhan, A.; MacDonald, M. A.; Zuin, L.; Fernández, J.; Palacios, A.; Martín, F.

    2012-01-01

    Dissociative photoionization (DPI) of randomly oriented H2 molecules has been studied using linearly polarized synchrotron radiation at selected photon energies of 31, 33, and 35 eV. Large amplitude oscillations in the photoelectron asymmetry parameter β, as a function of electron energy, have been observed. The phase of these β oscillations are in excellent agreement with the results of recent close coupling calculations [Fernández and Martín, New J. Phys. 11, 043020 (2009)NJOPFM1367-263010.1088/1367-2630/11/4/043020]. We show that the oscillations are the signature of interferences between the 1Q1Σu+1 and 1Q2Πu1 doubly excited states decaying at different internuclear distances. The oscillations thus provide information about the classical paths followed by the nuclei. The presence of such oscillations is predicted to be a general phenomenon in DPI.

  10. Photoionization and ion cyclotron resonance studies of the ion chemistry of ethylene oxide

    NASA Technical Reports Server (NTRS)

    Corderman, R. R.; Williamson, A. D.; Lebreton, P. R.; Buttrill, S. E., Jr.; Beauchamp, J. L.

    1976-01-01

    The formation of the ethylene oxide molecular ion and its subsequent ion-molecule reactions leading to the products C2H5O(+) and C3H5O(+) have been studied using time-resolved photoionization mass spectroscopy, ion cyclotron resonance spectroscopy, and photoelectron spectroscopy. An examination of the effects of internal energy on reactivity shows that the ratio of C3H5O(+) to C2H5O(+) increases by an order of magnitude with a single quantum of vibrational energy. The formation of (C2H4O/+/)-asterisk in a collision-induced isomerization is found which yields a ring-opened structure by C-C bond cleavage. The relaxed ring-opened C2H4O(+) ion reacts with neutral ethylene oxide by CH2(+) transfer to yield an intermediate product ion C3H6O(+) which gives C3H5O(+) by loss of H.

  11. 2008 Photoions, Photoionization & Photodetachment Gordon Research Conference January 27-February 1, 2008

    SciTech Connect

    Klaus Muller-Dethefs Nancy Ryan GRay

    2009-03-31

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

  12. Partial and total cross sections and multiplet structure in the photoionization of atomic manganese

    SciTech Connect

    Jimenez-Mier, J.; Krause, M.O.; Gerard, P. ); Hermsmeier, B.; Fadley, C.S.

    1989-10-01

    We determined the absolute partial photoionization cross section {sigma} and the angular distribution parameter {beta} of the 3{ital d}, 3{ital p}, and 3{ital s} photoelectrons in atomic manganese for 65{le}{ital h}{nu}{le}250 eV. The total photoionization cross section is in satisfactory accord with the single-particle Hartree-Slater calculation and in very good agreement with a relativistic time-dependent local-density-approximation calculation. Binding energies and intensity ratios of the 3{ital s}{sup {minus}1} and 3{ital p}{sup {minus}1} multiplet lines were obtained. Five lines were identified within the 3{ital p}{sup {minus}1} multiplet, and the measured spacings are close to those found in solid MnF{sub 2}. Similarly, the spacings in the 3{ital s}{sup {minus}1} multiplet are equal to the ones measured in solid MnF{sub 2}. There is good accord between our results for the angular-distribution parameter of the 3{ital p}{sup {minus}1} ({sup 7}P) line and those of Malutzki {ital et} {ital al}. (J. Phys. B 18, 1735 (1985)). The intensity ratios of {sup 5}P(1) to {sup 7}P and {sup 5}S(1) to {sup 7}S were seen to increase slowly somewhat above their thresholds. More rapid variations of all multiplet ratios were found within about 30 eV of threshold.

  13. Photoelectron spectra of 2-thiouracil, 4-thiouracil, and 2,4-dithiouracil

    NASA Astrophysics Data System (ADS)

    Ruckenbauer, Matthias; Mai, Sebastian; Marquetand, Philipp; González, Leticia

    2016-02-01

    Ground- and excited-state UV photoelectron spectra of thiouracils (2-thiouracil, 4-thiouracil, and 2,4-dithiouracil) have been simulated using multireference configuration interaction calculations and Dyson norms as a measure for the photoionization intensity. Except for a constant shift, the calculated spectrum of 2-thiouracil agrees very well with experiment, while no experimental spectra are available for the two other compounds. For all three molecules, the photoelectron spectra show distinct bands due to ionization of the sulphur and oxygen lone pairs and the pyrimidine π system. The excited-state photoelectron spectra of 2-thiouracil show bands at much lower energies than in the ground state spectrum, allowing to monitor the excited-state population in time-resolved UV photoelectron spectroscopy experiments. However, the results also reveal that single-photon ionization probe schemes alone will not allow monitoring all photodynamic processes existing in 2-thiouracil. Especially, due to overlapping bands of singlet and triplet states the clear observation of intersystem crossing will be hampered.

  14. Photoionization cross sections, electron-impact inverse mean free paths, and stopping powers for each subshell of silvera)

    NASA Astrophysics Data System (ADS)

    Lin, D. L.; Strickland, D. J.

    1980-03-01

    Using the Herman-Skillman potentials and bound wave functions for each subshell of silver, we have computed the continuum wave functions, and subshell-by-subshell photoionization cross sections with photoelectron energies up to 10 keV. Applying a relationship between photoionization and electron impact ionization, we have obtained inverse mean free paths and stopping powers, again by subshell, for electrons penetrating through silver. The maximum electron energy considered is 100 keV. For the total photoionization cross section, comparison of our work with experiment shows excellent agreement for photon energies down to 100 eV, below which solid-state effects should be included. Theoretical total inverse mean free paths, being strongly dominated by contributions from 4d electrons, are in good agreement with data around 1 keV, but about a factor of 2 larger at energies below 100eV. Our stopping power is in good agreement with other theoretical work above 400 eV and approaches the relativistic Bethe formula above 10 keV. Range is also computed and is in good agreement with other theoretical work.

  15. Double Photoionization of Aligned Molecular Hydrogen

    SciTech Connect

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

    2006-07-21

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

  16. K-shell photoionization cross-sections.

    NASA Technical Reports Server (NTRS)

    Daltabuit, E.; Cox, D. P.

    1972-01-01

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

  17. Photoionization of zinc by TDLDA calculations

    NASA Astrophysics Data System (ADS)

    Stener, M.; Decleva, P.

    1997-10-01

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

  18. Atomic photoionization experiment by harmonic-generation spectroscopy

    NASA Astrophysics Data System (ADS)

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

    2016-03-01

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

  19. Calculated photoionization cross sections using Quantemol-N

    NASA Astrophysics Data System (ADS)

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

    2015-06-01

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

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

    PubMed

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

    2007-12-13

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

  1. Time-resolved photoelectron spectroscopy of the CH{sub 3}I B{sup I}E 6s [2] state.

    SciTech Connect

    Thire, N.; Cireasa, R.; Blanchet, V.; Pratt, S. T.

    2010-01-01

    The predissociation dynamics of the vibrationless level of the 6s (B {sup 2}E) Rydberg state of CH{sub 3}I was studied by femtosecond-resolved velocity map imaging of photoelectrons. By monitoring the decay of the CH{sub 3}I{sup +} produced by photoionizing the B state, the predissociation lifetime was measured to be 1310 {+-} 70 fs. Photoelectron spectra were recorded as a function of the excitation scheme (one or two photons to the B state), and as a function of the ionizing wavelength. All of these photoelectron spectra show a simple time dependence that is consistent with the decay time of the CH{sub 3}I{sup +} ion signal. The photoelectron angular distributions for the ionization of the B state depend on the excitation scheme and the ionizing wavelength, and show a strong dependence on the vibrational modes excited in the resulting CH{sub 3}I{sup +}. At long delays, the photoelectron spectra are characterized by photoionization of the I({sup 2}P{sub 1/2}) fragment formed by predissociation of the B state.

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

    NASA Astrophysics Data System (ADS)

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

    2016-03-01

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

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

    SciTech Connect

    Not Available

    1994-01-01

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

  4. Well coincidence counting and analysis

    SciTech Connect

    Lu, Ming-Shih; Teichmann, T.; Ceo, R.N.; Collins, L.L.

    1994-03-01

    In several recent papers a physical/mathematical model was developed to describe the nuclear multiplicative processes in samples containing fissile material from a general statistical viewpoint, starting with the basic underlying physical phenomena. The results of this model agreed with the established picture used in ``standard`` HLNCC (High Level Neutron Coincidence Counter) measurements, but considerably extended them, and allowed a more detailed interpretation of the underlying physical mechanisms and of the higher moments of the neutron counts. The present paper examines some recent measurements made at Y-12 (Oak Ridge) using the AWCC, in the light of this model. The results show internal consistency under a variety of conditions, and give good agreement between experiment and theory.

  5. Concepts for Alpha Coincidence Detection

    SciTech Connect

    Warren, Glen A.; Dion, Michael P.; Miller, Brian W.; Tatishvili, Gocha

    2015-03-01

    The effectiveness of conventional measurement techniques for environmental monitoring is limited by background and other interferences. We are exploring a new measurement approach involving the detection of α particles in coincidence with conversion electrons as a means to simultaneously assay environmental samples for actinides without chemical separation. The initial target isotopes studied in this work are 238Pu, 239Pu, 240Pu and 241Am. We explore various aspects of the design, such as impact of the mounting of the source material, resolution requirements and impact of a background on isotopic uncertainties. We conclude that a dual gas proportional counter and a dual-sided, large-area silicon detector could provide similar performance for the measurement scenario examined.

  6. 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.

  7. Photoionization of hydroxymethyl (CD[sub 2]OH and CD[sub 2]OD) and methoxy (CD[sub 3]O) radicals. Photoion efficiency spectra, ionization energies, and thermochemistry

    SciTech Connect

    Kuo, S.C.; Zhang, Z.; Klemm, R.B. ); Liebman, J.F. ); Stief, L.J. ); Nesbitt, F.L. Coppin State College, Baltimore, MD )

    1994-04-14

    Photoion efficiency (PIE) spectra were obtained for CD[sub 2]OH, CD[sub 2]OD, and CD[sub 3]O radicals using the discharge flow-photoionization mass spectrometry technique. The radicals were generated in a flow tube via reaction of F atoms with the appropriate methanol isotopomers (CD[sub 3]OH [yields] CD[sub 2]OH, CD[sub 3]OD [yields] CD[sub 2]OD, and CD[sub 3]OH [yields] CD[sub 3]O), which were in large excess. Deuterated methoxy radicals, CD[sub 3]O, were also generated via the reaction of CD[sub 3] with NO[sub 2]. Photoionization of the radicals was achieved using high intensity, dispersed synchrotron radiation, and ionization energies (IE) of these radicals were derived from the thresholds of the PIE spectra: IE(CD[sub 2]OH) = 7.54 [+-] 0.02 eV, IE(CD[sub 2]OD) = 7.53 [+-] 0.02 eV, and IE(CD[sub 3]O) = 10.74 [+-] 0.02 eV. The PIE spectra for CD[sub 2]OH and CD[sub 3]O are compared to those of a previous photoionization study, and differences are discussed. Integration of previously published photoelectron spectroscopy data for CD[sub 2]OH yields a curve quite similar to our PIE spectrum. Empirical estimates of IE(CH[sub 2]OH) and IE(CH[sub 3]O) are given to corroborate our assignments. The measured ionization energies and the derived thermodynamic quantities are compared with previously reported results. 67 refs., 7 figs., 2 tabs.

  8. Gas-Phase Photoionization Of A Protein

    NASA Astrophysics Data System (ADS)

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

    2010-07-01

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

  9. Double photoionization of doubly-excited lithium

    NASA Astrophysics Data System (ADS)

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

    2012-06-01

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

  10. Electron correlation in beryllium: Effects in the ground state, short-pulse photoionization, and time-delay studies

    NASA Astrophysics Data System (ADS)

    Omiste, Juan J.; Li, Wenliang; Madsen, Lars Bojer

    2017-05-01

    We apply a three-dimensional implementation of the time-dependent restricted-active-space self-consistent-field (TD-RASSCF) method to investigate effects of electron correlation in the ground state of Be as well as in its photoionization dynamics by short XUV pulses, including time delay in photoionization. First, we obtain the ground state by propagation in imaginary time. We show that the flexibility of the TD-RASSCF on the choice of the active orbital space makes it possible to consider only relevant active space orbitals, facilitating the convergence to the ground state compared to the multiconfigurational time-dependent Hartree-Fock method, used as a benchmark to show the accuracy and efficiency of TD-RASSCF. Second, we solve the equations of motion to compute photoelectron spectra of Be after interacting with a short linearly polarized XUV laser pulse. We compare the spectra for different RAS schemes, and in this way we identify the orbital spaces that are relevant for an accurate description of the photoelectron spectra. Finally, we investigate the effects of electron correlation on the magnitude of the relative Eisenbud-Wigner-Smith (EWS) time delay in the photoionization process into two different ionic channels. One channel, the ground-state channel in the ion, is accessible without electron correlation. The other channel is only accessible when including electron correlation. For theory beyond the mean-field time-dependent Hartree-Fock, the EWS time delay for the photon energy analyzed is quite insensitive to the considered active orbital spaces.

  11. Extreme ultraviolet ionization of pure He nanodroplets: Mass-correlated photoelectron imaging, Penning ionization, and electron energy-loss spectra

    SciTech Connect

    Buchta, D.; Stienkemeier, F.; Mudrich, M.; Krishnan, S. R.; Moshammer, R.; Brauer, N. B.; Drabbels, M.; O’Keeffe, P.; Coreno, M.; Devetta, M.; Di Fraia, M.; Callegari, C.; Richter, R.; Prince, K. C.; Ullrich, J.

    2013-08-28

    The ionization dynamics of pure He nanodroplets irradiated by Extreme ultraviolet radiation is studied using Velocity-Map Imaging PhotoElectron-PhotoIon COincidence spectroscopy. We present photoelectron energy spectra and angular distributions measured in coincidence with the most abundant ions He{sup +}, He{sub 2}{sup +}, and He{sub 3}{sup +}. Surprisingly, below the autoionization threshold of He droplets, we find indications for multiple excitation and subsequent ionization of the droplets by a Penning-like process. At high photon energies we observe inelastic collisions of photoelectrons with the surrounding He atoms in the droplets.

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

    NASA Astrophysics Data System (ADS)

    Xie, Jinchun

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

  13. Photoelectron imaging following 2 + 1 multiphoton excitation of HBr.

    PubMed

    Romanescu, Constantin; Loock, Hans-Peter

    2006-07-07

    The photodissociation and photoionization dynamics of HBr via low-n Rydberg and ion-pair states was studied by using 2 + 1 REMPI spectroscopy and velocity map imaging of photoelectrons. Two-photon excitation at about 9.4-10 eV was used to prepare rotationally selected excited states. Following absorption of the third photon the unperturbed F (1)Delta(2) and i (3)Delta(2) states ionize directly into the ground vibrational state of the molecular ion according to the Franck-Condon principle and upon preservation of the ion core. In case of the V (1)Sigma(+)(0(+)) ion-pair state and the perturbed E (1)Sigma(+)(0(+)), g (3)Sigma(-)(0(+)), and H (1)Sigma(+)(0(+)) Rydberg states the absorption of the third photon additionally results in a long vibrational progression of HBr(+) in the X (2)Pi state as well as formation of electronically excited atomic photofragments. The vibrational excitation of the molecular ion is explained by autoionization of repulsive superexcited states into the ground state of the molecular ion. In contrast to HCl, the perturbed Rydberg states of HBr show strong participation of the direct ionization process, with ionic core preservation.

  14. Artifacts in digital coincidence timing

    SciTech Connect

    Moses, W. W.; Peng, Q.

    2014-10-16

    Digital methods are becoming increasingly popular for measuring time differences, and are the de facto standard in PET cameras. These methods usually include a master system clock and a (digital) arrival time estimate for each detector that is obtained by comparing the detector output signal to some reference portion of this clock (such as the rising edge). Time differences between detector signals are then obtained by subtracting the digitized estimates from a detector pair. A number of different methods can be used to generate the digitized arrival time of the detector output, such as sending a discriminator output into a time to digital converter (TDC) or digitizing the waveform and applying a more sophisticated algorithm to extract a timing estimator.All measurement methods are subject to error, and one generally wants to minimize these errors and so optimize the timing resolution. A common method for optimizing timing methods is to measure the coincidence timing resolution between two timing signals whose time difference should be constant (such as detecting gammas from positron annihilation) and selecting the method that minimizes the width of the distribution (i.e. the timing resolution). Unfortunately, a common form of error (a nonlinear transfer function) leads to artifacts that artificially narrow this resolution, which can lead to erroneous selection of the 'optimal' method. In conclusion, the purpose of this note is to demonstrate the origin of this artifact and suggest that caution should be used when optimizing time digitization systems solely on timing resolution minimization.

  15. Artifacts in Digital Coincidence Timing

    PubMed Central

    Moses, W. W.; Peng, Q.

    2014-01-01

    Digital methods are becoming increasingly popular for measuring time differences, and are the de facto standard in PET cameras. These methods usually include a master system clock and a (digital) arrival time estimate for each detector that is obtained by comparing the detector output signal to some reference portion of this clock (such as the rising edge). Time differences between detector signals are then obtained by subtracting the digitized estimates from a detector pair. A number of different methods can be used to generate the digitized arrival time of the detector output, such as sending a discriminator output into a time to digital converter (TDC) or digitizing the waveform and applying a more sophisticated algorithm to extract a timing estimator. All measurement methods are subject to error, and one generally wants to minimize these errors and so optimize the timing resolution. A common method for optimizing timing methods is to measure the coincidence timing resolution between two timing signals whose time difference should be constant (such as detecting gammas from positron annihilation) and selecting the method that minimizes the width of the distribution (i.e., the timing resolution). Unfortunately, a common form of error (a nonlinear transfer function) leads to artifacts that artificially narrow this resolution, which can lead to erroneous selection of the “optimal” method. The purpose of this note is to demonstrate the origin of this artifact and suggest that caution should be used when optimizing time digitization systems solely on timing resolution minimization. PMID:25321885

  16. A portable neutron coincidence counter

    SciTech Connect

    Peurrung, A.J.; Bowyer, S.M.; Craig, R.A.; Dudder, G.B.; Knopf, M.A.; Panisko, M.E.; Reeder, P.L.; Stromswold, D.C.; Sunberg, D.S.

    1996-11-01

    Pacific Northwest National Laboratory has designed and constructed a prototype portable neutron coincidence counter intended for use in a variety of applications, such as the verification and inspection of weapons components, safety measurements for novel and challenging situations, portable portal deployment to prevent the transportation of fissile materials, uranium enrichment measurements in hard-to-reach locations, waste assays for objects that cannot be measured by existing measurement systems, and decontamination and decommissioning. The counting system weighs less than 40 kg and is composed of parts each weighing no more than 5 kg. In addition, the counter`s design is sufficiently flexible to allow rapid, reliable assembly around containers of nearly arbitrary size and shape. The counter is able to discern the presence of 1 kg of weapons-grade plutonium within an ALR-8 (30-gal drum) in roughly 100 seconds and 10 g in roughly 1000 seconds. The counter`s electronics are also designed for maximum adaptability, allowing operation under a wide variety of circumstances, including exposure to gamma-ray fields of 1 R/h. This report provides a detailed review of the design and construction process. Finally, preliminary experimental measurements that confirm the performance capabilities of this counter are discussed. 6 refs., 18 figs., 3 tabs.

  17. Multiverse understanding of cosmological coincidences

    SciTech Connect

    Bousso, Raphael; Hall, Lawrence J.; Nomura, Yasunori

    2009-09-15

    There is a deep cosmological mystery: although dependent on very different underlying physics, the time scales of structure formation, of galaxy cooling (both radiatively and against the CMB), and of vacuum domination do not differ by many orders of magnitude, but are all comparable to the present age of the universe. By scanning four landscape parameters simultaneously, we show that this quadruple coincidence is resolved. We assume only that the statistical distribution of parameter values in the multiverse grows towards certain catastrophic boundaries we identify, across which there are drastic regime changes. We find order-of-magnitude predictions for the cosmological constant, the primordial density contrast, the temperature at matter-radiation equality, the typical galaxy mass, and the age of the universe, in terms of the fine structure constant and the electron, proton and Planck masses. Our approach permits a systematic evaluation of measure proposals; with the causal patch measure, we find no runaway of the primordial density contrast and the cosmological constant to large values.

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

    NASA Technical Reports Server (NTRS)

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

    1982-01-01

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

  19. A velocity map imaging spectrometer for electron?ion and ion?ion coincidence experiments with synchrotron radiation

    SciTech Connect

    Advanced Light Source; Kilcoyne, Arthur L; Rolles, D.; Pesic, Z.D.; Perri, M.; Bilodeau, R.C.; Ackerman, G.D.; Rude, B.S.; Kilcoyne, A.L.D.; Bozek, J.D.; Berrah, N.

    2007-04-27

    We have built a velocity imaging (VMI) spectrometer optimized for angle-resolved photoionization experiments with synchrotron radiation (SR) in the VUV and soft X-tay range. The spectrometer is equiped with four electrostatic lenses that focus the charged photoionization products onto a position-sensitive multi-hit delay-line anode. The use of two additional electrostatic lens elements as compared to the standard design of Eppink and Parker [T.J.B. Eppink and D.H. Parker, Rev. Sci. Instrum. 68 (1997) 3477]provides better focusing of an extended interaction region, which is crucial for most SR applications. Furthermore, the apparatus is equipped with a second micro-channel plate detector opposite to the VMI spectrometer, enabling electron-ion coincidence experiments and thereby mass-resolved ion spectroscopy independent of the time structure of the synchrotron radiation. First results for the photofragmentation of CO2 molecules are presented.

  20. Interference effect in the dipole and nondipole anisotropy parameters of the Kr 4p photoelectrons in the vicinity of the Kr (3d){sup -1{yields}}np resonant excitations

    SciTech Connect

    Ricz, S.; Ricsoka, T.; Holste, K.; Borovik, A. Jr.; Bernhardt, D.; Schippers, S.; Mueller, A.; Koever, A.; Varga, D.

    2010-04-15

    The angular distribution of the Kr 4p photoelectrons was investigated in the photon energy range of the (3d){sup -1{yields}}np resonant excitations. The experimental dipole ({beta}) and nondipole ({gamma} and {delta}) anisotropy parameters were determined for the spin-orbit components of the Kr 4p shell. A simple theoretical model was developed for the description of the photoionization and excitation processes. An interference effect was observed between the direct photoionization and the resonant excitation participator Auger decay processes in the photon energy dependence of the experimental anisotropy parameters.

  1. Dissociative photoionization mechanism of methanol isotopologues (CH3OH, CD3OH, CH3OD and CD3OD) by iPEPICO: energetics, statistical and non-statistical kinetics and isotope effects.

    PubMed

    Borkar, Sampada; Sztáray, Bálint; Bodi, Andras

    2011-07-28

    The dissociative photoionization of energy selected methanol isotopologue (CH(3)OH, CD(3)OH, CH(3)OD and CD(3)OD) cations was investigated using imaging Photoelectron Photoion Coincidence (iPEPICO) spectroscopy. The first dissociation is an H/D-atom loss from the carbon, also confirmed by partial deuteration. Somewhat above 12 eV, a parallel H(2)-loss channel weakly asserts itself. At photon energies above 15 eV, in a consecutive hydrogen molecule loss to the first H-atom loss, the formation of CHO(+)/CDO(+) dominates as opposed to COH(+)/COD(+) formation. We see little evidence for H-atom scrambling in these processes. In the photon energy range corresponding to the B[combining tilde] and C[combining tilde] ion states, a hydroxyl radical loss appears yielding CH(3)(+)/CD(3)(+). Based on the branching ratios, statistical considerations and ab initio calculations, this process is confirmed to take place on the first electronically excited Ã(2)A' ion state. Uncharacteristically, internal conversion is outcompeted by unimolecular dissociation due to the apparently weak Renner-Teller-like coupling between the X[combining tilde] and the à ion states. The experimental 0 K appearance energies of the ions CH(2)OH(+), CD(2)OH(+), CH(2)OD(+) and CD(2)OD(+) are measured to be 11.646 ± 0.003 eV, 11.739 ± 0.003 eV, 11.642 ± 0.003 eV and 11.737 ± 0.003 eV, respectively. The E(0)(CH(2)OH(+)) = 11.6454 ± 0.0017 eV was obtained based on the independently measured isotopologue results and calculated zero point effects. The 0 K heat of formation of CH(2)OH(+), protonated formaldehyde, was determined to be 717.7 ± 0.7 kJ mol(-1). This yields a 0 K heat of formation of CH(2)OH of -11.1 ± 0.9 kJ mol(-1) and an experimental 298 K proton affinity of formaldehyde of 711.6 ± 0.8 kJ mol(-1). The reverse barrier to homonuclear H(2)-loss from CH(3)OH(+) is determined to be 36 kJ mol(-1), whereas for heteronuclear H(2)-loss from CH(2)OH(+) it is found to be 210 kJ mol(-1).

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

    SciTech Connect

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

    2014-03-15

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

  3. Artifacts in digital coincidence timing

    DOE PAGES

    Moses, W. W.; Peng, Q.

    2014-10-16

    Digital methods are becoming increasingly popular for measuring time differences, and are the de facto standard in PET cameras. These methods usually include a master system clock and a (digital) arrival time estimate for each detector that is obtained by comparing the detector output signal to some reference portion of this clock (such as the rising edge). Time differences between detector signals are then obtained by subtracting the digitized estimates from a detector pair. A number of different methods can be used to generate the digitized arrival time of the detector output, such as sending a discriminator output into amore » time to digital converter (TDC) or digitizing the waveform and applying a more sophisticated algorithm to extract a timing estimator.All measurement methods are subject to error, and one generally wants to minimize these errors and so optimize the timing resolution. A common method for optimizing timing methods is to measure the coincidence timing resolution between two timing signals whose time difference should be constant (such as detecting gammas from positron annihilation) and selecting the method that minimizes the width of the distribution (i.e. the timing resolution). Unfortunately, a common form of error (a nonlinear transfer function) leads to artifacts that artificially narrow this resolution, which can lead to erroneous selection of the 'optimal' method. In conclusion, the purpose of this note is to demonstrate the origin of this artifact and suggest that caution should be used when optimizing time digitization systems solely on timing resolution minimization.« less

  4. Nondipole Effects in Double Photoionization of He

    SciTech Connect

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

    2006-01-09

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

  5. Double photoionization of tropone and cyclooctatetraene

    NASA Astrophysics Data System (ADS)

    Hartman, Tim; Wehlitz, Ralf

    2017-05-01

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

  6. GaAs-oxide interface states - Gigantic photoionization via Auger-like process

    NASA Technical Reports Server (NTRS)

    Lagowski, J.; Kazior, T. E.; Gatos, H. C.; Walukiewicz, W.; Siejka, J.

    1981-01-01

    Spectral and transient responses of photostimulated current in MOS structures were employed for the study of GaAs-anodic oxide interface states. Discrete deep traps at 0.7 and 0.85 eV below the conduction band were found with concentrations of 5 x 10 to the 12th/sq cm and 7 x 10 to the 11th/sq cm, respectively. These traps coincide with interface states induced on clean GaAs surfaces by oxygen and/or metal adatoms (submonolayer coverage). In contrast to surfaces with low oxygen coverage, the GaAs-thick oxide interfaces exhibited a high density (about 10 to the 14th/sq cm) of shallow donors and acceptors. Photoexcitation of these donor-acceptor pairs led to a gigantic photoionization of deep interface states with rates 1000 times greater than direct transitions into the conduction band. The gigantic photoionization is explained on the basis of energy transfer from excited donor-acceptor pairs to deep states.

  7. Electron localization following attosecond molecular photoionization.

    PubMed

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

    2010-06-10

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

  8. An R-matrix approach to electron-photon-molecule collisions: photoelectron angular distributions from aligned molecules

    NASA Astrophysics Data System (ADS)

    Harvey, Alex G.; Brambila, Danilo S.; Morales, Felipe; Smirnova, Olga

    2014-11-01

    We present a new extension of the UKRmol electron-molecule scattering code suite, which allows one to compute ab initio photoionization and photorecombination amplitudes for complex molecules, resolved both on the molecular alignment (orientation) and the emission angle and energy of the photoelectron. We illustrate our approach using CO2 as an example, and analyze the importance of multi-channel effects by performing our calculations at different, increasing levels of complexity. We benchmark our method by comparing the results of our calculations with experimental data and with theoretical calculations available in the literature.

  9. Photoelectron holography of platinum (111)

    SciTech Connect

    Petersen, B.L.; Terminello, L.J.; Barton, J.J.; Shirley, D.A.

    1993-04-01

    Platinum atoms near a (111) single-crystal face have been imaged using photoelectron holography. Electron angular intensity patterns were collected at equally spaced wavenumbers from 6 to 12{Angstrom}{sup {minus}1}. Images of atoms near expected atomic positions are obtained from single-wavenumber analyses over the range of the data set. Positions are detected further from the emitter than we have seen previously, and symmetry assumptions are not required. We have also adopted a three dimensional means of representing the data in order to help understand the results. Twin image suppression and artifact reduction in the holographically reconstructed data are set are obtained when images at different wavenumbers are correctly phase-summed. We are assessing the capability of the technique for rendering true three-dimensional structural information for unknown systems.

  10. Femtosecond photoelectron point projection microscope

    SciTech Connect

    Quinonez, Erik; Handali, Jonathan; Barwick, Brett

    2013-10-15

    By utilizing a nanometer ultrafast electron source in a point projection microscope we demonstrate that images of nanoparticles with spatial resolutions of the order of 100 nanometers can be obtained. The duration of the emission process of the photoemitted electrons used to make images is shown to be of the order of 100 fs using an autocorrelation technique. The compact geometry of this photoelectron point projection microscope does not preclude its use as a simple ultrafast electron microscope, and we use simple analytic models to estimate temporal resolutions that can be expected when using it as a pump-probe ultrafast electron microscope. These models show a significant increase in temporal resolution when comparing to ultrafast electron microscopes based on conventional designs. We also model the microscopes spectroscopic abilities to capture ultrafast phenomena such as the photon induced near field effect.

  11. High-frequency conductivity of photoionized plasma

    SciTech Connect

    Anakhov, M. V.; Uryupin, S. A.

    2016-08-15

    The tensor of the high-frequency conductivity of a plasma created via tunnel ionization of atoms in the field of linearly or circularly polarized radiation is derived. It is shown that the real part of the conductivity tensor is highly anisotropic. In the case of a toroidal velocity distribution of photoelectrons, the possibility of amplification of a weak high-frequency field polarized at a sufficiently large angle to the anisotropy axis of the initial nonequilibrium distribution is revealed.

  12. Photoelectron Spectroscopy of Substituted Phenylnitrenes

    NASA Astrophysics Data System (ADS)

    Wijeratne, Neloni R.; Fonte, Maria Da; Wenthold, Paul G.

    2009-06-01

    Nitrenes are unusual molecular structures with unfilled electronic valences that are isoelectronic with carbenes. Although, both can be generated by either thermal or photochemical decomposition of appropriate precursors they usually exhibit different reactivities. In this work, we carry out spectroscopic studies of substituted phenylnitrene to determine how the introduction of substituents will affect the reactivity and its thermochemical properties. All studies were carried out by using the newly constructed time-of-flight negative ion photoelectron spectrometer (NIPES) at Purdue University. The 355 nm photoelectron spectra of the o-, m-, and p-chlorophenyl nitrene anions are fairly similar to that measured for phenylnitrene anion. All spectra show low energy triplet state and a high energy singlet state. The singlet state for the meta isomer is well-resolved, with a well defined origin and observable vibrational structure. Whereas the singlet states for the ortho and para isomers have lower energy onsets and no resolved structure. The isomeric dependence suggests that the geometry differences result from the resonance interaction between the nitrogen and the substituent. Quinoidal resonance structures are possible for the open-shell singlet states of the o- and p-chlorinated phenyl nitrenes. The advantages of this type of electronic structures for the open-shell singlet states is that the unpaired electrons can be more localized on separate atoms in the molecules, minimizing the repulsion between. Because the meta position is not in resonance with the nitrenes, substitution at that position should not affect the structure of the open-shell singlet state. The measured electron affinities (EA) of the triplet phenylnitrenes are in excellent agreement with the values predicted by electronic structure calculations. The largest EA, 1.82 eV is found for the meta isomer, with para being the smallest, 1.70 eV.

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

    NASA Astrophysics Data System (ADS)

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

    2006-05-01

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

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

    NASA Astrophysics Data System (ADS)

    El-Gogary, Sameh R.

    2010-11-01

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

  15. Photoelectron emission as an alternative electron impact ionization source for ion trap mass spectrometry.

    PubMed

    Gamez, Gerardo; Zhu, Liang; Schmitz, Thomas A; Zenobi, Renato

    2008-09-01

    Electron impact ionization has several known advantages; however, heated filament electron sources have pressure limitations and their power consumption can be significant for certain applications, such as in field-portable instruments. Herein, we evaluate a VUV krypton lamp as an alternative source for ionization inside the ion trap of a mass spectrometer. The observed fragmentation patterns are more characteristic of electron impact ionization than photoionization. In addition, mass spectra of analytes with ionization potentials higher than the lamp's photon energy (10.6 eV) can be easily obtained. A photoelectron impact ionization mechanism is suggested by the observed data allowed by the work function of the ion trap electrodes (4.5 eV), which is well within the lamp's photon energy. In this case, the photoelectrons emitted at the surface of the ion trap end-cap electrode are accelerated by the applied rf field to the ring electrode. This allows the photoelectrons to gain sufficient energy to ionize compounds with high ionization potentials to yield mass spectra characteristic of electron impact. In this manner, electron impact ionization can be used in ion trap mass spectrometers at low powers and without the limitations imposed by elevated pressures on heated filaments.

  16. Study of selected benzyl azides by UV photoelectron spectroscopy and mass spectrometry

    NASA Astrophysics Data System (ADS)

    Pinto, R. M.; Olariu, R. I.; Lameiras, J.; Martins, F. T.; Dias, A. A.; Langley, G. J.; Rodrigues, P.; Maycock, C. D.; Santos, J. P.; Duarte, M. F.; Fernandez, M. T.; Costa, M. L.

    2010-09-01

    Benzyl azide and the three methylbenzyl azides were synthesized and characterized by mass spectrometry (MS) and ultraviolet photoelectron spectroscopy (UVPES). The electron ionization fragmentation mechanisms for benzyl azide and their methyl derivatives were studied by accurate mass measurements and linked scans at constant B/ E. For benzyl azide, in order to clarify the fragmentation mechanism, labelling experiments were performed. From the mass analysis of methylbenzyl azides isomers it was possible to differentiate the isomers ortho, meta and para. The abundance and nature of the ions resulting from the molecular ion fragmentation, for the three distinct isomers of substituted benzyl azides, were rationalized in terms of the electronic properties of the substituent. Concerning the para-isomer, IRC calculations were performed at UHF/6-31G(d) level. The photoionization study of benzyl azide, with He(I) radiation, revealed five bands in the 8-21 eV ionization energies region. From every photoelectron spectrum of methylbenzyl azides isomers it has been identified seven bands, on the same range as the benzyl azide. Interpretation of the photoelectron spectra was accomplished applying Koopmans' theorem to the SCF orbital energies obtained at HF/6-311++G(d, p) level.

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

    SciTech Connect

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

    2014-11-15

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

  18. An Atomic Photoionization Experiment by Harmonic Generation Spectroscopy

    NASA Astrophysics Data System (ADS)

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

    2016-05-01

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

  19. From Mere Coincidences to Meaningful Discoveries

    ERIC Educational Resources Information Center

    Griffiths, Thomas L.; Tenenbaum, Joshua B.

    2007-01-01

    People's reactions to coincidences are often cited as an illustration of the irrationality of human reasoning about chance. We argue that coincidences may be better understood in terms of rational statistical inference, based on their functional role in processes of causal discovery and theory revision. We present a formal definition of…

  20. Sensitivity to coincidences and paranormal belief.

    PubMed

    Hadlaczky, Gergö; Westerlund, Joakim

    2011-12-01

    Often it is difficult to find a natural explanation as to why a surprising coincidence occurs. In attempting to find one, people may be inclined to accept paranormal explanations. The objective of this study was to investigate whether people with a lower threshold for being surprised by coincidences have a greater propensity to become believers compared to those with a higher threshold. Participants were exposed to artificial coincidences, which were formally defined as less or more probable, and were asked to provide remarkability ratings. Paranormal belief was measured by the Australian Sheep-Goat Scale. An analysis of the remarkability ratings revealed a significant interaction effect between Sheep-Goat score and type of coincidence, suggesting that people with lower thresholds of surprise, when experiencing coincidences, harbor higher paranormal belief than those with a higher threshold. The theoretical aspects of these findings were discussed.

  1. Molecular-orbital decomposition of the ionization continuum for a diatomic molecule by angle- and energy-resolved photoelectron spectroscopy. I. Formalism

    NASA Astrophysics Data System (ADS)

    Park, Hongkun; Zare, Richard N.

    1996-03-01

    A theoretical formalism is developed for the quantum-state-specific photoelectron angular distributions (PADs) from the direct photoionization of a diatomic molecule in which both the ionizing state and the state of the ion follow Hund's case (b) coupling. The formalism is based on the molecular-orbital decomposition of the ionization continuum and therefore fully incorporates the molecular nature of the photoelectron-ion scattering within the independent electron approximation. The resulting expression for the quantum-state-specific PADs is dependent on two distinct types of dynamical quantities, one that pertains only to the ionization continuum and the other that depends both on the ionizing state and the ionization continuum. Specifically, the electronic dipole-moment matrix element rlλ exp(iηlλ) for the ejection of a photoelectron with orbital angular momentum quantum number l making a projection λ on the internuclear axis is expressed as ΣαλŪlαλλ exp (iπτ¯αλλ) Mαλλ, where Ūλ is the electronic transformation matrix, τ¯αλλ is the scattering phase shift associated with the αλth continuum molecular orbital, and Mαλλ is the real electronic dipole-moment matrix element that connects the ionizing orbital to the αλth continuum molecular orbital. Because Ūλ and τ¯αλλ depend only on the dynamics in the ionization continuum, this formalism allows maximal exploitation of the commonality between photoionization processes from different ionizing states. It also makes possible the direct experimental investigation of scattering matrices for the photoelectron-ion scattering and thus the dynamics in the ionization continuum by studying the quantum-state-specific PADs, as illustrated in the companion article on the photoionization of NO.

  2. Vacuum ultraviolet photoionization of carbohydrates and nucleotides

    SciTech Connect

    Shin, Joong-Won; Bernstein, Elliot R.

    2014-01-28

    Carbohydrates (2-deoxyribose, ribose, and xylose) and nucleotides (adenosine-, cytidine-, guanosine-, and uridine-5{sup ′}-monophosphate) are generated in the gas phase, and ionized with vacuum ultraviolet photons (VUV, 118.2 nm). The observed time of flight mass spectra of the carbohydrate fragmentation are similar to those observed [J.-W. Shin, F. Dong, M. Grisham, J. J. Rocca, and E. R. Bernstein, Chem. Phys. Lett. 506, 161 (2011)] for 46.9 nm photon ionization, but with more intensity in higher mass fragment ions. The tendency of carbohydrate ions to fragment extensively following ionization seemingly suggests that nucleic acids might undergo radiation damage as a result of carbohydrate, rather than nucleobase fragmentation. VUV photoionization of nucleotides (monophosphate-carbohydrate-nucleobase), however, shows that the carbohydrate-nucleobase bond is the primary fragmentation site for these species. Density functional theory (DFT) calculations indicate that the removed carbohydrate electrons by the 118.2 nm photons are associated with endocyclic C–C and C–O ring centered orbitals: loss of electron density in the ring bonds of the nascent ion can thus account for the observed fragmentation patterns following carbohydrate ionization. DFT calculations also indicate that electrons removed from nucleotides under these same conditions are associated with orbitals involved with the nucleobase-saccharide linkage electron density. The calculations give a general mechanism and explanation of the experimental results.

  3. Extreme ultraviolet-induced photoionized plasmas

    NASA Astrophysics Data System (ADS)

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

    2014-05-01

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

  4. Cooling and Heating Functions of Photoionized Gas

    NASA Astrophysics Data System (ADS)

    Gnedin, Nickolay Y.; Hollon, Nicholas

    2012-10-01

    Cooling and heating functions of cosmic gas are crucial ingredients for any study of gas dynamics and thermodynamics in the interstellar and intergalactic media. As such, they have been studied extensively in the past under the assumption of collisional ionization equilibrium. However, for a wide range of applications, the local radiation field introduces a non-negligible, often dominant, modification to the cooling and heating functions. In the most general case, these modifications cannot be described in simple terms and would require a detailed calculation with a large set of chemical species using a radiative transfer code (the well-known code Cloudy, for example). We show, however, that for a sufficiently general variation in the spectral shape and intensity of the incident radiation field, the cooling and heating functions can be approximated as depending only on several photoionization rates, which can be thought of as representative samples of the overall radiation field. This dependence is easy to tabulate and implement in cosmological or galactic-scale simulations, thus economically accounting for an important but rarely included factor in the evolution of cosmic gas. We also show a few examples where the radiation environment has a large effect, the most spectacular of which is a quasar that suppresses gas cooling in its host halo without any mechanical or non-radiative thermal feedback.

  5. Intergalactic magnetogenesis at Cosmic Dawn by photoionization

    NASA Astrophysics Data System (ADS)

    Durrive, J.-B.; Langer, M.

    2015-10-01

    We present a detailed analysis of an astrophysical mechanism that generates cosmological magnetic fields during the Epoch of Reionization. It is based on the photoionization of the intergalactic medium by the first sources formed in the Universe. First the induction equation is derived, then the characteristic length and time-scales of the mechanism are identified, and finally numerical applications are carried out for first stars, primordial galaxies and distant powerful quasars. In these simple examples, the strength of the generated magnetic fields varies between the order of 10-23 G on hundreds of kiloparsecs and 10-19 G on hundreds of parsecs in the neutral intergalactic medium between the Strömgren spheres of the sources. Thus, this mechanism contributes to the premagnetization of the whole Universe before large-scale structures are in place. It operates with any ionizing source, at any time during the Epoch of Reionization. Finally, the generated fields possess a characteristic spatial configuration which may help discriminate these seeds from those produced by different mechanisms.

  6. Vacuum ultraviolet photoionization of carbohydrates and nucleotides

    NASA Astrophysics Data System (ADS)

    Shin, Joong-Won; Bernstein, Elliot R.

    2014-01-01

    Carbohydrates (2-deoxyribose, ribose, and xylose) and nucleotides (adenosine-, cytidine-, guanosine-, and uridine-5'-monophosphate) are generated in the gas phase, and ionized with vacuum ultraviolet photons (VUV, 118.2 nm). The observed time of flight mass spectra of the carbohydrate fragmentation are similar to those observed [J.-W. Shin, F. Dong, M. Grisham, J. J. Rocca, and E. R. Bernstein, Chem. Phys. Lett. 506, 161 (2011)] for 46.9 nm photon ionization, but with more intensity in higher mass fragment ions. The tendency of carbohydrate ions to fragment extensively following ionization seemingly suggests that nucleic acids might undergo radiation damage as a result of carbohydrate, rather than nucleobase fragmentation. VUV photoionization of nucleotides (monophosphate-carbohydrate-nucleobase), however, shows that the carbohydrate-nucleobase bond is the primary fragmentation site for these species. Density functional theory (DFT) calculations indicate that the removed carbohydrate electrons by the 118.2 nm photons are associated with endocyclic C-C and C-O ring centered orbitals: loss of electron density in the ring bonds of the nascent ion can thus account for the observed fragmentation patterns following carbohydrate ionization. DFT calculations also indicate that electrons removed from nucleotides under these same conditions are associated with orbitals involved with the nucleobase-saccharide linkage electron density. The calculations give a general mechanism and explanation of the experimental results.

  7. Core-Hole Molecular Frame X-Ray Photoelectron Angular Distributions as Molecular Geometry Probes

    NASA Astrophysics Data System (ADS)

    Trevisan, Cynthia; Williams, Joshua; Menssen, Adrian; Weber, Thorsten; Rescigno, Thomas; McCurdy, Clyde; Landers, Allen

    2014-05-01

    We present experimental and theoretical results for the angular dependence of electrons ejected from the core orbitals of ethane (C2H6) and tetrafluoromethane (CF4) in an effort to understand the origin of the imaging effect by which the molecular frame photoelectron angular distributions (MFPADs) for removing an electron from a 1s orbital effectively image the geometry of a class of molecules. At low energies, our calculations predict the same imaging effect in X2H6 previously found in CH4, H2O and NH3. By contrast, in experiment and calculations CF4 displays an anti-imaging effect, whereby the electron ejected by core photoionization has the tendency to avoid molecular bonds, if averaged over directions of polarization of the incident X-ray beam. Our measurements employ the COLTRIMS method and the calculations were performed with the Complex Kohn Variational method.

  8. Vibrational branching ratios in the photoelectron spectra of N2 and CO: interference and diffraction effects.

    PubMed

    Plésiat, Etienne; Decleva, Piero; Martín, Fernando

    2012-08-21

    We present a detailed account of existing theoretical methods specially designed to provide vibrationally resolved photoionization cross sections of simple molecules within the Born-Oppenheimer approximation, with emphasis on newly developed methods based on density functional theory. The performance of these methods is shown for the case of N(2) and CO photoionization. Particular attention is paid to the region of high photon energies, where the electron wavelength is comparable to the bond length and, therefore, two-center interferences and diffraction are expected to occur. As shown in a recent work [Canton et al., Proc. Natl. Acad. Sci. U. S. A., 2011, 108, 7302-7306], the main experimental difficulty, which is to extract the relatively small diffraction features from the rapidly decreasing cross section, can be easily overcome by determining ratios of vibrationally resolved photoelectron spectra and existing theoretical calculations. From these ratios, one can thus get direct information about the molecular geometry. In this work, results obtained in a wide range of photon energies and for many different molecular orbitals of N(2) and CO are discussed and compared with the available experimental measurements. From this comparison, limitations and further possible improvements of the existing theoretical methods are discussed. The new results presented in the manuscript confirm that the conclusions reported in the above reference are of general validity.

  9. Redesign of the GATE PET coincidence sorter

    NASA Astrophysics Data System (ADS)

    Strydhorst, Jared; Buvat, Irène

    2016-09-01

    The GATE software platform, based on the Geant4 toolkit for simulating particle interactions with matter, enables simulation of, among other medical imaging and treatment systems, positron emission tomography. However, at least one publication (Moraes et al 2015 Phys. Med. 31 43-8) has reported discrepancies between the expected results and those obtained using GATE simulations, specifically with respect to the coincidence sorter which processes single events detected by the scanner to find coincidence pairs. In particular, the current software appears to overestimate the number of ‘true’ coincidence pairs when in multi-window mode, while the delayed coincidence window, used to estimate the randoms present in the prompt coincidence window, underestimates the randoms. Both effects are particularly evident at high count rates. We have investigated this discrepancy and reproduced the reported problems. We have also rewritten the relevant portion of the GATE code to correct the issue. In this note we describe the modifications to the coincidence sorter and repeat the simulations which previously showed unexpected results. Some discrepancies remain in the estimation of the randoms with the single-window mode which are a consequence of the algorithm itself. In multi-window mode however, the simulation agrees exactly with the expected results. The modifications to the coincidence sorter code will be incorporated into the next release of GATE (> version 7.2).

  10. Experimental Investigations of the Lunar Photoelectron Sheath

    NASA Astrophysics Data System (ADS)

    Dove, A.; Sternovsky, Z.; Wang, X.; Robertson, S. H.; Lapanse, C.; Horanyi, M.; Collette, A.

    2010-12-01

    Solar ultraviolet radiation incident upon the dayside lunar surface produces a photoelectron gas that dominates the near-surface plasma environment, with a typical density of 60 cm-3 and a characteristic scale-length of ~1 m. It has traditionally been difficult to produce a photoelectron gas with sufficient density in a laboratory settings to study its properties. In our initial experiments, the characterization of the photoelectron density above a Zr surface (work function W=4.4 eV) illuminated by Xe excimer lamps (peak emission at a wavelength of 172 nm) indicated that a sheath with a Debye length on the order of 10 cm formed. We characterize the photoelectron population above the surface by utilizing an emissive probe to map the electric potential distribution above the surface, and a Langmuir probe to determine the number density and temperature of the photoelectrons. A grid is placed 7.5 cm above the Zr surface to repel photoelectrons emitted from the chamber walls. Emissive probe measurements show a potential dip of about 2 V extending ~1 cm above the zirconium surface. The size of this potential well is dependent on the number of lamps illuminating the surface, as the density of photoelectrons above the surface increases with greater illumination. The electrons in the sheath have a Maxwellian distribution with an electron temperature around 1 eV (maximum energies are expected to be approximately 2.8 eV). We will use this experimental apparatus to characterize the photoelectron sheath above other surfaces; powders, such as CeO2 have similar work functions, but different photoelectric yields. Lunar soil simulants are expected to have approximately an order of magnitude smaller yield than metallic surfaces, which will act to increase the characteristic length of the photoelectron sheath above the surface. The experiments and accompanying computer simulations are used to guide the development of new instrument concepts for future in situ plasma measurements on

  11. Experimental and ab initio characterization of HC3N(+) vibronic structure. I. Synchrotron-based threshold photo-electron spectroscopy.

    PubMed

    Desrier, Antoine; Romanzin, Claire; Lamarre, Nicolas; Alcaraz, Christian; Gans, Bérenger; Gauyacq, Dolores; Liévin, Jacques; Boyé-Péronne, Séverine

    2016-12-21

    Threshold-photoionization spectroscopy of cyanoacetylene (HC3N) and its (15)N isotopologue has been investigated in the vacuum-ultraviolet range with a synchrotron-based experiment allowing to record threshold-photoelectron spectrum and photoion yield over a large energy range (from 88 500 to 177 500 cm(-1), i.e., from 11 to 22 eV). Adiabatic ionization energies towards the three lowest electronic states X(+)(2)Π, A(+) Σ+2, and B(+) Π2 are derived from the threshold-photoelectron spectrum. A detailed description of the vibrational structure of these states is proposed leading to the determination of the vibrational frequencies for most modes. The vibrational assignments and the discussion about the electronic structure are supported by multireference ab initio calculations (CASPT2, MRCI). Unprecedented structures are resolved and tentatively assigned in the region of the B(+)← X transition. Exploratory calculations highlight the complexity of the electronic landscape of the cation up to approximately 10 eV above its ground state.

  12. Prominent conjugate processes in the PCI recapture of photoelectrons revealed by high resolution Auger electron measurements of Xe

    NASA Astrophysics Data System (ADS)

    Azuma, Yoshiro; Kosugi, Satoshi; Suzuki, Norihiro; Shigemasa, Eiji; Iwayama, Hiroshi; Koike, Fumihiro

    2016-05-01

    The Xe (N5O2 , 3O2 , 3) Auger electron spectrum originating from 4d5/ 2 - 1 photoionization was measured with the photon energy tuned very close above the ionization threshold. As the photon energy approached the 4d5/ 2 - 1 photoionization threshold, Rydberg series structures including several angular momentum components were formed within the Auger profile by the recapture of the photoelectrons into high-lying final ion orbitals. Our spectrum with resolution much narrower than the lifetime width of the corresponding core excited state allowed us to resolve detailed structures due to the orbital angular momenta very clearly. Unexpectedly, conjugate peaks originating from the exchange of angular momentum between the photoelectron and the Auger electron through Post-Collision-Interaction were found to dominate the spectrum. The new assignments were in accord with the quantum defect values obtained for the high Rydberg series for singly charged ionic Xe + 5 p(1S0) ml. This work was supported by Japan Society for the Promotion of Science through Grants-in-Aid for Scientific Research No. 23600009.

  13. Experimental and ab initio characterization of HC3N+ vibronic structure. I. Synchrotron-based threshold photo-electron spectroscopy

    NASA Astrophysics Data System (ADS)

    Desrier, Antoine; Romanzin, Claire; Lamarre, Nicolas; Alcaraz, Christian; Gans, Bérenger; Gauyacq, Dolores; Liévin, Jacques; Boyé-Péronne, Séverine

    2016-12-01

    Threshold-photoionization spectroscopy of cyanoacetylene (HC3N) and its 15N isotopologue has been investigated in the vacuum-ultraviolet range with a synchrotron-based experiment allowing to record threshold-photoelectron spectrum and photoion yield over a large energy range (from 88 500 to 177 500 cm-1, i.e., from 11 to 22 eV). Adiabatic ionization energies towards the three lowest electronic states X+ 2Π, A+ +2Σ, and B+ 2Π are derived from the threshold-photoelectron spectrum. A detailed description of the vibrational structure of these states is proposed leading to the determination of the vibrational frequencies for most modes. The vibrational assignments and the discussion about the electronic structure are supported by multireference ab initio calculations (CASPT2, MRCI). Unprecedented structures are resolved and tentatively assigned in the region of the B+← X transition. Exploratory calculations highlight the complexity of the electronic landscape of the cation up to approximately 10 eV above its ground state.

  14. Coincidence lattices in the hyperbolic plane.

    PubMed

    Rodríguez-Andrade, M A; Aragón-González, G; Aragón, J L; Gómez-Rodríguez, A

    2011-01-01

    The problem of coincidences of lattices in the space R(p,q), with p + q = 2, is analyzed using Clifford algebra. We show that, as in R(n), any coincidence isometry can be decomposed as a product of at most two reflections by vectors of the lattice. Bases and coincidence indices are constructed explicitly for several interesting lattices. Our procedure is metric-independent and, in particular, the hyperbolic plane is obtained when p = q = 1. Additionally, we provide a proof of the Cartan-Dieudonné theorem for R(p,q), with p + q = 2, that includes an algorithm to decompose an orthogonal transformation into a product of reflections.

  15. Photo-Ionization and Photo-Dissociation of Trapped PAH Cations

    NASA Astrophysics Data System (ADS)

    Joblin, Christine; Zhen, Junfeng; Rodriguez Castillo, Sarah; Mulas, Giacomo; Sabbah, Hassan; Simon, Aude; Giuliani, Alexandre; Nahon, Laurent; Martin, Serge; Champeaux, Jean-Philippe; Mayer, Paul M.

    2016-06-01

    In astrophysical environments, polycyclic aromatic hydrocarbons (PAHs) are submitted to VUV photons of energy up to ˜20 eV. In the laboratory, photoelectron-photoion spectroscopy is usually performed using VUV synchrotron radiation, in which the same photon (15-25 eV), is used to ionize and dissociate PAHs. These experiments explore specific conditions and complementary studies in ion traps are required for a wider investigation of interstellar conditions. We have used the LTQ linear ion trap available on the DESIRS VUV beamline at SOLEIL to study the interaction of PAH cations with photons in the 7-20 eV range. We recorded by action spectroscopy the relative intensities of photo-fragmentation and photo-ionization of eight PAH cations ranging in size from 14 to 24 carbon atoms and with different structures. We found that, at photon energies below ˜13.6 eV, fragmentation dominates for the smaller species, while for larger species ionization is competitive immediately above the second ionization potential. At higher photon energies, all species behave similarly, the ionization yield gradually increases, levelling off between 0.8 and 0.9 at ˜18 eV. We have also recorded the competition between the different dissociation channels as a function of the VUV photon energy, such as the C_2H_2 versus H/H_2 loss. We will discuss how these data can be compared to results of photoelectron spectroscopy performed on neutral PAHs at the VUV beamline at the Swiss Light Source. H.W. Jochims et al., Astron. & Astrophys. 420 (1994), 307-317; P. M. Mayer et al., J. Chem. Phys. 134 (2011), 244312-244312-8 J. Zhen et al., Astron. & Astrophys. (2016), in press B. West et al., J. Phys. Chem. A 118 (2014), 7824-7831; B. West et al., J. Phys. Chem. A 118 (2014), 9870-9878 Acknowledgments: European Research Council grant ERC-2013-SyG, Grant Agreement n. 610256 NANOCOSMOS.

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

    NASA Astrophysics Data System (ADS)

    Nahar, Sultana N.

    2012-06-01

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

  17. Galaxy formation with local photoionization feedback - I. Methods

    NASA Astrophysics Data System (ADS)

    Kannan, R.; Stinson, G. S.; Macciò, A. V.; Hennawi, J. F.; Woods, R.; Wadsley, J.; Shen, S.; Robitaille, T.; Cantalupo, S.; Quinn, T. R.; Christensen, C.

    2014-01-01

    We present a first study of the effect of local photoionizing radiation on gas cooling in smoothed particle hydrodynamics simulations of galaxy formation. We explore the combined effect of ionizing radiation from young and old stellar populations. The method computes the effect of multiple radiative sources using the same tree algorithm as used for gravity, so it is computationally efficient and well resolved. The method foregoes calculating absorption and scattering in favour of a constant escape fraction for young stars to keep the calculation efficient enough to simulate the entire evolution of a galaxy in a cosmological context to the present day. This allows us to quantify the effect of the local photoionization feedback through the whole history of a galaxy's formation. The simulation of a Milky Way-like galaxy using the local photoionization model forms ˜40 per cent less stars than a simulation that only includes a standard uniform background UV field. The local photoionization model decreases star formation by increasing the cooling time of the gas in the halo and increasing the equilibrium temperature of dense gas in the disc. Coupling the local radiation field to gas cooling from the halo provides a preventive feedback mechanism which keeps the central disc light and produces slowly rising rotation curves without resorting to extreme feedback mechanisms. These preliminary results indicate that the effect of local photoionizing sources is significant and should not be ignored in models of galaxy formation.

  18. Coincident indices of exons and introns.

    PubMed

    Xu, J; Chen, R; Ling, L; Shen, R; Sun, J

    1993-07-01

    In this paper, the coincident index, proposed by W. F. Friedman in cryptology, is made use of in DNA sequence analysis and exon prediction. The coincident index of exons exceeds that of introns by many times, and is mainly affected by window length, which is correlated negatively with the coincident index. An optimal exon prediction scheme was obtained by experimental analysis with an orthogonal table. Besides exons, many other special sites such as tandem repeats can be identified by using the coincident index approach. The application of this approach to the ARV-2 (AIDS associated retrovirus 2) genome found three new possible coding regions and some unusual base composition regions which are probably related to definite biological functions.

  19. Space and Time Resolved Continuum Correlation in the Post-Collision Interaction of Core-Photoionized Neon

    NASA Astrophysics Data System (ADS)

    Bhandary, A.; Landers, A. L.; Robicheaux, F.; Osipov, T.; Hertlein, M.; Prior, M. H.; Belkacem, A.; Ranitovic, P.; Bocharova, I.; Cocke, C. L.; Jahnke, T.; Schoffler, M.; Titze, J.; Dorner, R.

    2007-06-01

    We have used the COLTRIMS^* technique to measure the momentum distribution of the photoelectron and the recoil ion produced by the core-photoionization of neon. Conservation of momentum allows us to determine the subsequent auger electron's momentum that is emitted when the Ne^+ relaxes to the Ne^2+ state. Momentum space plots of the electrons and the recoil ion are then used to resolve the three-body correlated post-collision interactions in space and time. Finally, classical calculations have been performed which corroborate our interpretation of the experimental results. ^*R. Dorner, V. Mergel, O. Jagutzki, L. Spielberger, J. Ull- rich, R. Moshammer, and H. Schmidt-B"aocking. Physics Reports, 330:96-192, 2000.

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

    NASA Astrophysics Data System (ADS)

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

    2017-09-01

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

  1. Determining activities of radionuclides from coincidence signatures

    NASA Astrophysics Data System (ADS)

    Warren, Glen A.; Smith, L. Eric; Aalseth, Craig E.; Ellis, Edward; Hossbach, Todd W.; Valsan, Andrei B.

    2006-05-01

    The spectral analysis of simultaneously observed photons in separate detectors may provide an invaluable tool for radioisotope identification applications. A general recursive method to determine the activity of an isotope from the observed coincidence signature rate is discussed. The method coherently accounts for effects of true coincidence summing within a single detector and detection efficiencies. A verification of the approach with computer simulations is also discussed.

  2. Photoionization spectroscopy of nucleobases and analogues in the gas phase using synchrotron radiation as excitation light source.

    PubMed

    Schwell, Martin; Hochlaf, Majdi

    2015-01-01

    We review here the photoionization and photoelectron spectroscopy of the gas phase nucleic acid bases adenine, thymine, uracil, cytosine, and guanine, as well as the three base analogues 2-hydroxyisoquinoline, 2-pyridone, and δ-valerolactam in the vacuum ultraviolet (VUV) spectral regime. The chapter focuses on experimental work performed with VUV synchrotron radiation and related ab initio quantum chemical calculations of higher excited states beyond the ionization energy. After a general part, where experimental and theoretical techniques are described in detail, key results are presented by order of growing complexity in the spectra of the molecules. Here we concentrate on (1) the accurate determination of ionization energies of isolated gas phase NABs and investigation of the vibrational structure of involved ionic states, including their mutual vibronic couplings, (2) the treatment of tautomerism after photoionization, in competition with other intramolecular processes, (3) the study of fragmentation of these molecular systems at low and high internal energies, and (4) the study of the evolution of the covalent character of hydrogen bonding upon substitution, i.e., examination of electronic effects (acceptor, donor, etc.).

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

    NASA Astrophysics Data System (ADS)

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

    2014-05-01

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

  4. Characterization of Photoelectron Emission for SGEMP Analysis.

    DTIC Science & Technology

    1980-05-01

    solar-cell cover glass 17 Normalized photoelectron spectral data from Mylar, 44 Teflon and two thicknesses of Kapton 18 Photoelectron signals from flat...silver, glass, copper, 63 Teflon /Thick Kapton and Mylar/Thin Mylar irradiated by OWL II aluminum-wire spectrum. Uncertainties are discussed in text 27...experiments; these included gold, silver, anodized aluminum, thick Kapton, thick Teflon , white thermal paint and solar cell covers. The other samples were

  5. Photoelectronic Sensor with Gold Nanoparticle Plasmon Antenna

    DTIC Science & Technology

    2016-07-20

    AFRL-AFOSR-JP-TR-2016-0081 Photoelectronic Sensor with Gold Nanoparticle Plasmon Antenna Yukiharu Uraoka NARA INSTITUTE OF SCIENCE AND TECHNOLOGY...REPORT TYPE Final 3. DATES COVERED (From - To) 17 Jul 2014 to 16 Jan 2016 4. TITLE AND SUBTITLE Photoelectronic Sensor with Gold Nanoparticle Plasmon...utilizing gold nanoparticles (GNPs), which are supposed to function not only as the Plasmon antenna but also as the sensing part. The photocurrent in the

  6. Multiphoton Ionization Mass and Photoelectron Spectroscopy.

    DTIC Science & Technology

    1984-07-01

    narro , band. tunable. frequency doubled dye laser Their relative importance depend% on the sample being studied ha- led to an cnormou, improcment in...block number) Mult iphoton Ionization Photoelectron Spectroscopy Laser Induced Ionization Ultraviolet Laser Radiation ft ArITAcr (camthIe i rvee ehl N...molecular ions generated by laser ionization have been monitored. Using a time of flight photoelectron spectrometer, the kinetic energy distribution of the

  7. Design of Laboratory Experiments to Study Photoionization Fronts

    NASA Astrophysics Data System (ADS)

    Gray, William James; Davis, Josh; Drake, R. Paul

    2017-06-01

    Here we present the theoretical foundation for a laboratory experiment to study photoionization fronts. Photoionization fronts play important roles in the formation and evolution of structure in the Universe. A properly designed experiment will have to control the recombination rate, electron impact ionization rate, and the initial thermal spectrum. We show that such an experiment can be designed, but requires the use of the largest high-energy-density laser facilities, such as Omega, Z, and NIF. We also show that prior experiments do not actually generate photoionization fronts, rather a heat front is produced by heat conductions. We show some initial simulation results of the current experimental design and characterize the ionization front.

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

    NASA Astrophysics Data System (ADS)

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

    2015-01-01

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

  9. Depth-resolved subcycle dynamics of photoionization in solids

    NASA Astrophysics Data System (ADS)

    Zhokhov, P. A.; Zheltikov, A. M.

    2017-09-01

    We develop a theoretical framework for the analysis of ultrafast dynamics of photoionization in solids that treats the electron density buildup resolved within the field cycle jointly with the propagation dynamics of the laser driver. We show that while the standard, cycle-averaging photoionization models predict a monotonic buildup of the electron density within the driver pulse, the cycle-resolved photoionization model used in this work reveals a subcycle modulation of optical properties of a solid, giving rise to complex patterns of reflected and transmitted fields and providing a source for optical harmonic generation. Propagation effects are shown to heavily distort the spectra of high-order harmonics. Still, the analysis of harmonic spectra and the temporal structure of the harmonic field reveals physically significant properties of the nonlinear-optical response, suggesting the existence of attosecond bursts of interband optical-harmonic emission.

  10. Simulation of triple coincidences in PET.

    PubMed

    Cal-González, J; Lage, E; Herranz, E; Vicente, E; Udias, J M; Moore, S C; Park, M-A; Dave, S R; Parot, V; Herraiz, J L

    2015-01-07

    Although current PET scanners are designed and optimized to detect double coincidence events, there is a significant amount of triple coincidences in any PET acquisition. Triple coincidences may arise from causes such as: inter-detector scatter (IDS), random triple interactions (RT), or the detection of prompt gamma rays in coincidence with annihilation photons when non-pure positron-emitting radionuclides are used (β(+)γ events). Depending on the data acquisition settings of the PET scanner, these triple events are discarded or processed as a set of double coincidences if the energy of the three detected events is within the scanner's energy window. This latter option introduces noise in the data, as at most, only one of the possible lines-of-response defined by triple interactions corresponds to the line along which the decay occurred. Several novel works have pointed out the possibility of using triple events to increase the sensitivity of PET scanners or to expand PET imaging capabilities by allowing differentiation between radiotracers labeled with non-pure and pure positron-emitting radionuclides. In this work, we extended the Monte Carlo simulator PeneloPET to assess the proportion of triple coincidences in PET acquisitions and to evaluate their possible applications. We validated the results of the simulator against experimental data acquired with a modified version of a commercial preclinical PET/CT scanner, which was enabled to acquire and process triple-coincidence events. We used as figures of merit the energy spectra for double and triple coincidences and the triples-to-doubles ratio for different energy windows and radionuclides. After validation, the simulator was used to predict the relative quantity of triple-coincidence events in two clinical scanners assuming different acquisition settings. Good agreement between simulations and preclinical experiments was found, with differences below 10% for most of the observables considered. For clinical

  11. Dynamics of photoionization of hydrogenlike ions in Debye plasmas

    SciTech Connect

    Qi, Y. Y.; Wang, J. G.; Janev, R. K.

    2009-12-15

    Photoionization processes for the ground state and n<=3 excited states of hydrogenlike ions embedded in a weakly coupled plasma are investigated in the entire energy range of a nonrelativistic regime. The plasma screening of the Coulomb interaction between charged particles is described by the Debye-Hueckel model. The energy levels and wave functions for both the bound and continuum states are calculated by solving the Schroedinger equation numerically by the symplectic integrator. The screening of Coulomb interactions reduces the number of bound electron states, decreases their binding energies, broadens the radial distribution of electron wave functions of these states, and changes significantly the phases and the amplitudes of continuum wave functions. These changes strongly affect the dipole matrix elements between the bound and continuum states and, hence, the photoionization cross sections. The most significant effects of the screened Coulomb interactions on the energy behavior of photoionization cross sections are manifested in its low-energy behavior (Wigner threshold law), the appearance of multiple shape and virtual-state resonances when the energy levels of upper bound states enter the continuum after certain critical strength of the screening, and in the (slight) reduction of the cross section at high photon energies. All these features of the photoionization cross section are related to the short-range character of the Debye-Hueckel potential. The effects of the potential screening on the Combet-Farnoux and Cooper minima in the photoionization cross section are also investigated. Comparison of calculated photoionization cross sections with the results of other authors, when available, is made.

  12. Photoionization and fragmentation of H3O+ under XUV irradiation

    NASA Astrophysics Data System (ADS)

    Domesle, C.; Dziarzhytski, S.; Guerassimova, N.; Harbo, L. S.; Heber, O.; Lammich, L.; Jordon-Thaden, B.; Treusch, R.; Wolf, A.; Pedersen, H. B.

    2013-10-01

    The photolysis of the hydronium cation H3O+ has been studied at the extreme ultraviolet wavelengths of 35.56±0.24 nm (34.87±0.24 eV) and 21.85±0.17 nm (56.74±0.44 eV) using a crossed ion-photon beam setup at the free-electron laser FLASH. Coincidence photoelectron and photofragment spectroscopy was performed at 21.85 nm, where both inner and outer valence ionization are allowed, and revealed that the XUV photolysis of H3O+ is by far dominated by ionization of outer valence electrons forming the 1A1 and 2E states of the dication H3O2+. The dications were found to dissociate into the channels H2O++H+ (72±4%), OH0+2H+ (18±6%), and OH++H++H0 (10±1%). A kinematic analysis of the H2O++H+ channel after photoabsorption at 35.56 nm (where only outer valence ionization is possible) showed dissociation into excited states of the water radical ion, where the 1A1 state breaks up into the linear Ã2A1 state of H2O+ and the 2E state decays into the strongly bent B˜2B2 state. Finally, from the 2E state of H3O2+, dissociation into OH0(X2Π)+2H+ was identified to occur with a near linear dissociation geometry.

  13. Relativistic theory of the double photoionization of heliumlike atoms

    SciTech Connect

    Yerokhin, Vladimir A.; Surzhykov, Andrey

    2011-09-15

    A fully relativistic calculation of the double photoionization of heliumlike atoms is presented. The approach is based on the partial-wave representation of the Dirac continuum states and accounts for the retardation in the electron-electron interaction as well as the higher-order multipoles of the absorbed photon. The electron-electron interaction is taken into account to the leading order of the perturbation theory. The relativistic effects are shown to become prominent already for the medium-Z ions, changing the shape and the asymptotic behavior of the photon energy dependence of the ratio of the double-to-single photoionization cross section.

  14. Photoionization spectrum of the B2A' state of HCO

    NASA Astrophysics Data System (ADS)

    Foltynowicz, Robert J.; Rupp, Wolfgang; Hedderich, Hartmut G.; Grant, Edward R.

    1999-12-01

    Formyl radicals, excited to specific rovibrational levels of the strongly bent B2A' state are photoionized to form vibrationally excited states of the linear cation by the absorption of a tunable pulse of ultraviolet light from a second laser. Strong and essentially continuous photoionization spectra, which appear at intervals lying 7000 and 12 000 cm -1 above the adiabatic threshold, establish that formyl radicals can be efficiently ionized with a large geometry change at both energies. Non-Franck-Condon intensities suggest multiquantum pathways for vibrational autoionization.

  15. Double K-shell photoionization and universal scaling laws

    NASA Astrophysics Data System (ADS)

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

    2009-11-01

    The photon energy dependence of the double K-shell ionization cross sections for light atoms and He-like ions is reported. The K-shell double photoionization DPI cross-sections for hollow atom production are compared to those of the corresponding He-like counterparts. The relative contribution of the initial-state correlations and final-state electron-electron interactions to the K-shell DPI is addressed. A semiempirical universal scaling of the double photoionization cross sections with the effective nuclear charge for neutral atoms in the range 2 <= Z <= 47 is established.

  16. Absolute Photoionization Cross Sections of Two Cyclic Ketones: Cyclopentanone & Cyclohexanone.

    PubMed

    Price, Chelsea; Fathi, Yasmin; Meloni, Giovanni

    2017-02-23

    Absolute photoionization cross sections for cyclopentanone and cyclohexanone, as well as partial ionization cross sections for the dissociative ionized fragments, are presented in this investigation. Experiments are performed via a multiplexed photoionization mass spectrometer utilizing VUV synchrotron radiation supplied by the Advanced Light Source of Lawrence Berkeley National Laboratory. These results allow the quantification of these species that is relevant to investigate the kinetics and combustion reactions of potential biofuels. The CBS-QB3 calculated values for the adiabatic ionization energies agree well with the experimental values and the identification of possible dissociative fragments is discussed for both systems.

  17. Atmospheric pressure photoionization using tunable VUV synchrotron radiation

    NASA Astrophysics Data System (ADS)

    Giuliani, A.; Giorgetta, J.-L.; Ricaud, J.-P.; Jamme, F.; Rouam, V.; Wien, F.; Laprévote, O.; Réfrégiers, M.

    2012-05-01

    We report here the first coupling of an atmospheric pressure photoionization (APPI) source with a synchrotron radiation beamline in the vacuum ultra-violet (VUV). A commercial APPI source of a QStar Pulsar i from AB Sciex was modified to receive photons from the DISCO beamline at the SOLEIL synchrotron radiation facility. Photons are delivered at atmospheric pressure in the 4-20 eV range. The advantages of this new set up, termed SR-APPI, over classical APPI are spectral purity and continuous tunability. The technique may also be used to perform tunable photoionization mass spectrometry on fragile compounds difficult to vaporize by classical methods.

  18. Photoelectron momentum distributions of molecules in bichromatic circularly polarized attosecond UV laser fields

    NASA Astrophysics Data System (ADS)

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

    2016-05-01

    We theoretically investigate molecular photoelectron momentum distributions (MPMDs) by bichromatic [frequencies (ω1,ω2)] circularly polarized attosecond UV laser pulses. Simulations performed on aligned single-electron H2+ by numerically solving the corresponding three-dimensional time-dependent Schrödinger equation within a static nucleus frame show that MPMDs exhibit a spiral structure for both co-rotating and counter-rotating schemes. Results are analyzed by attosecond perturbation ionization models. Coherent electron wave packets created, respectively, by the two color pulses in the continuum interfere with each other. Photoionization distributions are functions of the photoelectron momentum p and the ejection angle θ , thus leading to spiral MPMDs. The dependence of spiral MPMDs on the time delay between the bicircular pulses and their relative phases is also presented. The spiral interference patterns are determined by the helicities and frequencies (ω1,ω2 ) of the bicircular fields. It is also found that the spiral patterns are sensitive to the molecular alignment and suppressed by two-center ionization interference, thus offering new tools for imaging molecular geometry.

  19. High-resolution pulsed-field ionization photoelectron study of O{sub 2}

    SciTech Connect

    Hsu, C.W.; Evans, M.; Stimson, S.

    1997-04-01

    There have been numerous photoionization studies of O{sub 2} over the past 10 years. Using the pulsed field ionization (PFI) photoelectron spectroscopy (PES) technique, the electronic ground state of O{sub 2}{sup +} (X{sup 2}{Pi}{sub g}{sup {minus}}) has been well studied on the rotationally resolved level by several groups. However, due to the difficulty of producing photon energies above 18 eV using the tunable lasers, the electronic excited states of O{sub 2}{sup +} have been mostly studied on the vibrationally resolved level using the threshold photoelectron spectroscopy (TPES) and the synchrotron radiation. Recently, the authors developed a new technique for performing the PFI-PE experiments using multi-bunch synchrotron radiation at the Chemical Dynamics Beamline of the Advanced Light Source (ALS). Using the high resolution VUV light from the ALS, they have obtained the PFI-PE spectra of O{sub 2} between 12 and 24 eV. In this abstract, the authors report for the first time the rotationally resolved spectra of O{sub 2}{sup +} (b{sup 4}{Sigma}{sub g}{sup {minus}}, v{sup +}=0).

  20. Ambipolar Electric Field, Photoelectrons, and Their Role in Atmospheric Escape From Hot Jupiters

    NASA Technical Reports Server (NTRS)

    Cohen, O.; Glocer, A.

    2012-01-01

    Atmospheric mass loss from Hot Jupiters can be large due to the close proximity of these planets to their host star and the strong radiation the planetary atmosphere receives. On Earth, a major contribution to the acceleration of atmospheric ions comes from the vertical separation of ions and electrons, and the generation of the ambipolar electric field. This process, known as the "polar wind," is responsible for the transport of ionospheric constituents to Earth's magnetosphere, where they are well observed. The polar wind can also be enhanced by a relatively small fraction of super-thermal electrons (photoelectrons) generated by photoionization.We formulate a simplified calculation of the effect of the ambipolar electric field and the photoelectrons on the ion scale height in a generalized manner. We find that the ion scale height can be increased by a factor of 2-15 due to the polar wind effects. We also estimate a lower limit of an order of magnitude increase of the ion density and the atmospheric mass-loss rate when polar wind effects are included.

  1. Multi-reference approach to the calculation of photoelectron spectra including spin-orbit coupling

    SciTech Connect

    Grell, Gilbert; Bokarev, Sergey I. Kühn, Oliver; Winter, Bernd; Seidel, Robert; Aziz, Emad F.; Aziz, Saadullah G.

    2015-08-21

    X-ray photoelectron spectra provide a wealth of information on the electronic structure. The extraction of molecular details requires adequate theoretical methods, which in case of transition metal complexes has to account for effects due to the multi-configurational and spin-mixed nature of the many-electron wave function. Here, the restricted active space self-consistent field method including spin-orbit coupling is used to cope with this challenge and to calculate valence- and core-level photoelectron spectra. The intensities are estimated within the frameworks of the Dyson orbital formalism and the sudden approximation. Thereby, we utilize an efficient computational algorithm that is based on a biorthonormal basis transformation. The approach is applied to the valence photoionization of the gas phase water molecule and to the core ionization spectrum of the [Fe(H{sub 2}O){sub 6}]{sup 2+} complex. The results show good agreement with the experimental data obtained in this work, whereas the sudden approximation demonstrates distinct deviations from experiments.

  2. AMBIPOLAR ELECTRIC FIELD, PHOTOELECTRONS, AND THEIR ROLE IN ATMOSPHERIC ESCAPE FROM HOT JUPITERS

    SciTech Connect

    Cohen, O.; Glocer, A.

    2012-07-01

    Atmospheric mass loss from Hot Jupiters can be large due to the close proximity of these planets to their host star and the strong radiation the planetary atmosphere receives. On Earth, a major contribution to the acceleration of atmospheric ions comes from the vertical separation of ions and electrons, and the generation of the ambipolar electric field. This process, known as the 'polar wind', is responsible for the transport of ionospheric constituents to Earth's magnetosphere, where they are well observed. The polar wind can also be enhanced by a relatively small fraction of super-thermal electrons (photoelectrons) generated by photoionization. We formulate a simplified calculation of the effect of the ambipolar electric field and the photoelectrons on the ion scale height in a generalized manner. We find that the ion scale height can be increased by a factor of 2-15 due to the polar wind effects. We also estimate a lower limit of an order of magnitude increase of the ion density and the atmospheric mass-loss rate when polar wind effects are included.

  3. Nonadiabatic Dynamics May Be Probed through Electronic Coherence in Time-Resolved Photoelectron Spectroscopy.

    PubMed

    Bennett, Kochise; Kowalewski, Markus; Mukamel, Shaul

    2016-02-09

    We present a hierarchy of Fermi golden rules (FGRs) that incorporate strongly coupled electronic/nuclear dynamics in time-resolved photoelectron spectroscopy (TRPES) signals at different levels of theory. Expansion in the joint electronic and nuclear eigenbasis yields the numerically most challenging exact FGR (eFGR). The quasistatic Fermi Golden Rule (qsFGR) neglects nuclear motion during the photoionization process but takes into account electronic coherences as well as populations initially present in the pumped matter as well as those generated internally by coupling between electronic surfaces. The standard semiclassical Fermi Golden Rule (scFGR) neglects the electronic coherences and the nuclear kinetic energy during the ionizing pulse altogether, yielding the classical Condon approximation. The coherence contributions depend on the phase-profile of the ionizing field, allowing coherent control of TRPES signals. The photoelectron spectrum from model systems is simulated using these three levels of theory. The eFGR and the qsFGR show temporal oscillations originating from the electronic or vibrational coherences generated as the nuclear wave packet traverses a conical intersection. These oscillations, which are missed by the scFGR, directly reveal the time-evolving splitting between electronic states of the neutral molecule in the curve-crossing regime.

  4. Photoionization of helium by attosecond pulses: Extraction of spectra from correlated wave functions

    NASA Astrophysics Data System (ADS)

    Argenti, Luca; Pazourek, Renate; Feist, Johannes; Nagele, Stefan; Liertzer, Matthias; Persson, Emil; Burgdörfer, Joachim; Lindroth, Eva

    2013-05-01

    We investigate the photoionization spectrum of helium by attosecond XUV pulses both in the spectral region of doubly excited resonances as well as above the double ionization threshold. In order to probe for convergence, we compare three techniques to extract photoelectron spectra from the wave packet resulting from the integration of the time-dependent Schrödinger equation in a finite-element discrete variable representation basis. These techniques are projection on products of hydrogenic bound and continuum states, projection onto multichannel scattering states computed in a B-spline close-coupling basis, and a technique based on exterior complex scaling implemented in the same basis used for the time propagation. These methods allow one to monitor the population of continuum states in wave packets created with ultrashort pulses in different regimes. Applications include photo cross sections and anisotropy parameters in the spectral region of doubly excited resonances, time-resolved photoexcitation of autoionizing resonances in an attosecond pump-probe setting, and the energy and angular distribution of correlated wave packets for two-photon double ionization.

  5. Nondipole effects in the triply differential cross section for double photoionization of He

    SciTech Connect

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

    2005-05-15

    Lowest-order nondipole effects are studied systematically in double photoionization (DPI) of the He atom. Ab initio parametrizations of the quadrupole transition amplitude for DPI from the {sup 1}S{sub 0} state are presented in terms of the exact two-electron radial matrix elements. Analytic expressions for these matrix elements within lowest-order perturbation theory (LOPT) in the interelectron interaction are also given. The corresponding parametrizations for the dipole-quadrupole triply differential cross section (TDCS) are presented for the case of an elliptically polarized photon. A general analysis of retardation-induced asymmetries of the TDCS including the circular dichroism effect at equal energy sharing is presented. Numerical LOPT estimates of nondipole asymmetries in photoelectron angular distributions for the cases of linear and circular polarization and of the circular dichroism effect at equal energy sharing are presented. We find that experimental observation of nondipole effects at excess energies of the order of tens to hundreds of eV should be feasible in TDCS measurements. Our numerical results exhibit a nondipole forward-backward asymmetry in the TDCS for DPI of He at an excess energy of 450 eV that is in qualitative agreement with existing experimental data.

  6. Inner-Shell Photoionization: Teijo A˚berg's Concept of RRRS

    NASA Astrophysics Data System (ADS)

    Armen, G. Bradley

    2003-01-01

    Teijo Åberg died on December 29, 2000 — and with his passing we have lost a gifted and important member of our community. Over the years Teijo has made many major contributions to the science of x-ray and inner-shell physics. Perhaps the most visionary of these was his idea of radiative and radiationless resonant Raman scattering (RRRRS) [1]. This arose as an outgrowth of his earlier thoughts on Auger [2] and x-ray [3] processes. It is visionary in that it attempts to unify the various aspects of inner-shell photoexcitation and decay as different aspects of the same basic process, i.e. resonant inelastic x-ray scattering. In honor and memory of Teijo, and as a last attempt to promote his ideas, I describe here the theory and some of its consequences. First, RRRRS is outlined in a semi-rigorous form, with emphasis placed on the physical nature of the concepts. Then, using the example of atomic K-shell photoionization, we see how features such as fluorescence and photoelectron lines arise in a natural way as manifestations of resonance scattering.

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

    NASA Astrophysics Data System (ADS)

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

    1995-08-01

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

  8. Photoelectrons observed in the polar wind

    NASA Astrophysics Data System (ADS)

    Kitamura, N.; Seki, K.; Nishimura, T.; Terada, N.; Ono, T.; Hori, T.; Strangeway, R. J.; McFadden, J. P.; Carlson, C. W.

    2011-12-01

    We have statistically examined photoelectron spectra in the polar cap obtained by the electron spectrometer aboard the Fast Auroral SnapshoT (FAST) satellite at about 3800 km altitude during geomagnetically quiet periods at solar maximum. The geomagnetically quiet periods is defined as the times when the Kp index is less than or equal to 2+ for the preceding 3 hours and when the SYM-H index ranges from -10 to 40 nT. The polar cap is defined by the lack of energetic ions [Andersson et al., 2004]. The data obtained during geomagnetically quiet periods in July 2002 are used for the statistical study. In this period, the apogee of the FAST satellite was located at high latitudes in the Northern (summer) Hemisphere. We found counter-streaming photoelectrons of up to more than 10 eV, indicating existence of a potential drop above the satellite altitude. Such distributions were frequently (more than 80% in occurrence frequency) observed in the polar cap. The estimated typical potential drop above the satellite is about 20 V, which is about a half of that predicted by photoelectron-driven polar wind models with a potential drop at high altitudes (about 7 RE) [Wilson et al., 1997; Su et al., 1998]. The net number flux of escaping photoelectrons negatively correlates with the magnitude of the potential drop. On the other hand, the net escape flux also negatively correlates with the number flux of upgoing photoelectrons. Since the flux of the escaping photoelectrons should be equal to the flux of the polar wind ions under the condition of the zero field-aligned current, this negative correlation indicates that the larger number flux of upgoing photoelectrons correspond to weaker polar wind. This fact seems to disagree with the idea that photoelectrons drive the polar wind, which was suggested by the modeling studies [e.g., Tam et al., 1998]. These results imply that relation between photoelectrons and the polar wind is not as simple as that predicted by modeling studies.

  9. Coincidence imaging system with electron optics

    NASA Astrophysics Data System (ADS)

    Kroupa, Martin; Jakubek, Jan; Krejci, Frantisek; Zemlicka, J.; Horacek, M.; Radlicka, T.; Vlcek, I.

    2011-05-01

    As a part of multiple-detector system for coincidence instrumental neutron activation analysis (CINAA) a new method which includes a devoted electron optic unit has been built. In order to achieve higher sensitivity, enhanced contrast and higher spatial resolution the new coincidence imaging arrangement newly incorporates to electron optic unit, source, the gamma detector and the Timepix electron detector. The electron optic unit can be configured for different electron energies. The description of the assembled apparatus, calibration and performance for different electron energies are presented.

  10. On Points of Coincidence of Two Mappings

    NASA Astrophysics Data System (ADS)

    Davidjan, V. R.

    1981-02-01

    This paper is devoted to the coincidence theory of two continuous mappings.A definition is given, in cohomological terms, of the coincidence index I_{f, g} of two continuous mappings f, g \\colon M \\to N, where M and N are connected (not necessarily compact), orientable, n-dimensional topological manifolds without boundary, f is a compact mapping and g is a proper mapping.Invariance of the index I_{f, g} under compact homotopies of f and proper homotopies of g is proved. It is shown that I_{f, g} \

  11. Protonation enhancement by dichloromethane doping in low-pressure photoionization

    NASA Astrophysics Data System (ADS)

    Shu, Jinian; Zou, Yao; Xu, Ce; Li, Zhen; Sun, Wanqi; Yang, Bo; Zhang, Haixu; Zhang, Peng; Ma, Pengkun

    2016-12-01

    Doping has been used to enhance the ionization efficiency of analytes in atmospheric pressure photoionization, which is based on charge exchange. Compounds with excellent ionization efficiencies are usually chosen as dopants. In this paper, we report a new phenomenon observed in low-pressure photoionization: Protonation enhancement by dichloromethane (CH2Cl2) doping. CH2Cl2 is not a common dopant due to its high ionization energy (11.33 eV). The low-pressure photoionization source was built using a krypton VUV lamp that emits photons with energies of 10.0 and 10.6 eV and was operated at ~500–1000 Pa. Protonation of water, methanol, ethanol, and acetaldehyde was respectively enhanced by 481.7 ± 122.4, 197.8 ± 18.8, 87.3 ± 7.8, and 93.5 ± 35.5 times after doping 291 ppmv CH2Cl2, meanwhile CH2Cl2 almost does not generate noticeable ions itself. This phenomenon has not been documented in the literature. A new protonation process involving in ion-pair and H-bond formations was proposed to expound the phenomenon. The observed phenomenon opens a new prospect for the improvement of the detection efficiency of VUV photoionization.

  12. Protonation enhancement by dichloromethane doping in low-pressure photoionization

    PubMed Central

    Shu, Jinian; Zou, Yao; Xu, Ce; Li, Zhen; Sun, Wanqi; Yang, Bo; Zhang, Haixu; Zhang, Peng; Ma, Pengkun

    2016-01-01

    Doping has been used to enhance the ionization efficiency of analytes in atmospheric pressure photoionization, which is based on charge exchange. Compounds with excellent ionization efficiencies are usually chosen as dopants. In this paper, we report a new phenomenon observed in low-pressure photoionization: Protonation enhancement by dichloromethane (CH2Cl2) doping. CH2Cl2 is not a common dopant due to its high ionization energy (11.33 eV). The low-pressure photoionization source was built using a krypton VUV lamp that emits photons with energies of 10.0 and 10.6 eV and was operated at ~500–1000 Pa. Protonation of water, methanol, ethanol, and acetaldehyde was respectively enhanced by 481.7 ± 122.4, 197.8 ± 18.8, 87.3 ± 7.8, and 93.5 ± 35.5 times after doping 291 ppmv CH2Cl2, meanwhile CH2Cl2 almost does not generate noticeable ions itself. This phenomenon has not been documented in the literature. A new protonation process involving in ion-pair and H-bond formations was proposed to expound the phenomenon. The observed phenomenon opens a new prospect for the improvement of the detection efficiency of VUV photoionization. PMID:27905552

  13. Helium 23S photoionization up to the N = 5 threshold

    NASA Astrophysics Data System (ADS)

    Argenti, Luca; Moccia, Roberto

    2008-02-01

    We present the results of an accurate B-spline K-matrix calculation of total and partial cross sections and asymmetry parameters for the photoionization of the metastable 23Se state of helium up to the N = 5 threshold. The effect of the [040]+5 intruder state below N = 4 is shown.

  14. Photodissociation of Acetaldehyde and the Photoionization Cross Section of HCO

    NASA Astrophysics Data System (ADS)

    Shubert, V. Alvin; Pratt, Stephen T.

    2010-06-01

    Acetaldehyde was photodissociated with near UV laser light, and the methyl (CH_3) and formyl (HCO) radical fragments were photoionized with vacuum ultraviolet (VUV) light. The fragments were detected by using both time of flight mass spectrometry and velocity ion map imaging. With the former technique, simultaneous detection of both fragments provided the intensity of HCO+ relative to CH_3+ with I(HCO+)/I(CH_3+) ≈ 0.8. Because the absolute photoionization cross section of the CH_3 radical has been characterized (≈ 5 Mb) at the VUV energies of interest, the absolute photoionization cross section of HCO could be determined from the intensity ratio, yielding an HCO cross section of ≈ 4 Mb at 10.3 eV. However, because some of the HCO fragments could be formed with enough internal energy to undergo secondary dissociation, velocity ion map imaging was employed to determine the extent of any secondary dissociation that occurred. The translational energy distributions obtained for both the CH_3 and HCO fragments are nearly identical, indicating that no HCO fragments underwent secondary dissociation. A surprising result was the smaller photoionization cross section of HCO relative to CH_3. Comparison to the isoelectronic species of NO will be discussed and a potential explanation will be offered for this observation. This work was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences under contract No. DE-AC02-06CH11357.

  15. Atomic kinetics of a neon photoionized plasma experiment at Z

    NASA Astrophysics Data System (ADS)

    Mayes, Daniel C.; Mancini, Roberto; E Bailey, James; Loisel, Guillaume; Rochau, Gregory

    2017-06-01

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

  16. Dissociative photoionization of ethyl acrylate: Theoretical and experimental insights

    NASA Astrophysics Data System (ADS)

    Song, Yanlin; Chen, Jun; Ding, Mengmeng; Wei, Bin; Cao, Maoqi; Shan, Xiaobin; Zhao, Yujie; Huang, Chaoqun; Sheng, Liusi; Liu, Fuyi

    2015-08-01

    The photoionization and dissociation of ethyl acrylate have been investigated by time-of-flight mass spectrometer with tunable vacuum ultraviolet (VUV) source in the range of 9.0-20.0 eV. The photoionization mass spectrum (PIMS) for ethyl acrylate and photoionization efficiency (PIE) curves for its major fragment ions: C5H7O2+, C4H5O2+, C3H5O2+, C3H4O+, C3H3O+, C2H5O+, C2H3O+, C2H5+ and C2H4+ have been obtained. The formation channels of main fragments are predicted by Gaussian 09 program at G3B3 level and examined via their dissociation energies from experimental results. Based on our analysis, nine main dissociative photoionization channels are proposed: C5H7O2+ + H, C4H5O2+ + CH3, C3H5O2+ + C2H3, C3H4O+ + C2H4O, C3H3O+ + C2H5O, C2H5O+ + C3H3O, C2H3O+ + C3H5O, C2H5+ + C3H3O2, C2H4+ + C3H4O2, respectively. The results of this work lead to a better understanding of photochemistry in the environment.

  17. Electron scattering from and photoionization of open- shell atoms

    NASA Astrophysics Data System (ADS)

    Lin, Dong

    1999-09-01

    The multiconfiguration Hartree-Fock (MCHF) approach, developed by Dr. H. P. Saha et al, has been proved to be extremely successful in the past few years in reproducing experimental results at a very high level of accuracy. The research projects we are interested consist of two areas. In the first area we performed ab initio calculations on elastic scattering of electrons from open-shell sulfur atoms. In the second area, in order to understand the electronic dynamics in photoionization of atoms, we carried out accurate calculations on valence and K-shell photoionization of three-electron systems from lithium through neon for photon energies from threshold to very high energies; to further identify the autoionization resonances which were observed near threshold and to understand the dynamics, we modifies the MCHF method to include relativistic effects and performed calculation on partial photoionization cross section, resonance structure and effect of spin-orbit interaction in photoionization of atomic bromine. The calculated results obtained in each of these investigations are compared with available experimental and theoretical data and are found to be in very good agreement. The research contribution made for the fulfillment of the degree, we understand, will be a valuable addition towards a better understanding of the open-shell systems.

  18. Correlation Effects in the Photoionization of Confined Calcium and Zinc

    NASA Astrophysics Data System (ADS)

    Varma, R. Hari; Manson, S. T.

    2005-05-01

    Studies of atoms confined in an endohedral environment have aroused significant recent interest [1]. In this work, the photoionization @Ca and @Zn have been studied using the Relativistic-Random-Phase Approximation, modified to include the confinement potential. Photoionization of the 4s and 3p subshells of free and confined atomic calcium, along with the 4s, 3d, 3p and 3s subshells of free and confined atomic zinc, have been studied. The photoionization parameters of confined atoms differ significantly from those of their ``free'' counterparts. The dipole cross sections and angular distribution asymmetry parameters exhibit oscillations with energy arising from the back scattering of the escaping electron by the confining potential, i.e., ``confinement resonances'' [2]. These oscillations persist when nondipole matrix elements are also included as is reflected in the nondipole cross section and angular distribution asymmetry parameters [3]; the relative strengths of the oscillations due to back-scattering in the E1 and E2 photoionization parameters have qualitatively different profiles as a function of photon energy. [1] V. K. Dolmatov, A. S. Baltenkov, J.-P. Connerade and S. T. Manson, Radiation Phys. Chem. 70, 417 (2004). [2] M. Ya. Amusia, A. S. Baltenkov, V. K. Dolmatov, S. T. Manson and A. Z. Msezane, Phys. Rev. A 70, 023201 (2004). [3] P.C. Deshmukh, Tanima Banerjee, K. P. Sunanda and R. Hari Varma, Radiation Phys. and Chem (submitted).

  19. Photoionization of Ca XV with high energy features

    NASA Astrophysics Data System (ADS)

    Nahar, Sultana N.

    2017-02-01

    Photoionization cross sections of (Ca XV + hν → Ca XVI + e), with high energy resonant photo-absorption phenomena, of a large number of bound states, 701 in total with n ≤ 10 and l ≤ 9, are reported. They are obtained using the R-matrix method with a close coupling (CC) wavefunction expansion of 29 states of n = 2,3 complexes of the core ion Ca XVI. Characteristic features found in photoionization of the ion are illustrated with examples. The cross section (σPI) of the ground 2s22p2(3P) state is found to be unaffected by the size of the wavefunction expansion except for weak sparse resonances in high energy region. However, effects on excited states are considerable as the core excitations to n = 3 states are manifested in huge resonant absorption in high energy photoionization. They show existence of prominent high peak resonant features and enhancement in the background that were not studied before for Ca XV. In addition photoionization of the excited states with a single valence electron is dominated by Seaton resonant structures formed by the photo-excitation-of-core in the high energy region. These features will impact other quantities, such as the opacity, electron-ion recombination in high temperature plasmas where the ion exists, and hence will play important role in determination of elemental abundances in the astronomical objects.

  20. Protonation enhancement by dichloromethane doping in low-pressure photoionization.

    PubMed

    Shu, Jinian; Zou, Yao; Xu, Ce; Li, Zhen; Sun, Wanqi; Yang, Bo; Zhang, Haixu; Zhang, Peng; Ma, Pengkun

    2016-12-01

    Doping has been used to enhance the ionization efficiency of analytes in atmospheric pressure photoionization, which is based on charge exchange. Compounds with excellent ionization efficiencies are usually chosen as dopants. In this paper, we report a new phenomenon observed in low-pressure photoionization: Protonation enhancement by dichloromethane (CH2Cl2) doping. CH2Cl2 is not a common dopant due to its high ionization energy (11.33 eV). The low-pressure photoionization source was built using a krypton VUV lamp that emits photons with energies of 10.0 and 10.6 eV and was operated at ~500-1000 Pa. Protonation of water, methanol, ethanol, and acetaldehyde was respectively enhanced by 481.7 ± 122.4, 197.8 ± 18.8, 87.3 ± 7.8, and 93.5 ± 35.5 times after doping 291 ppmv CH2Cl2, meanwhile CH2Cl2 almost does not generate noticeable ions itself. This phenomenon has not been documented in the literature. A new protonation process involving in ion-pair and H-bond formations was proposed to expound the phenomenon. The observed phenomenon opens a new prospect for the improvement of the detection efficiency of VUV photoionization.

  1. Electronic structure of β-Ga{sub 2}O{sub 3} single crystals investigated by hard X-ray photoelectron spectroscopy

    SciTech Connect

    Li, Guo-Ling; Zhang, Fabi; Guo, Qixin; Cui, Yi-Tao; Oji, Hiroshi; Son, Jin-Young

    2015-07-13

    By combination of hard X-ray photoelectron spectroscopy (HAXPES) and first-principles band structure calculations, the electronic states of β-Ga{sub 2}O{sub 3} were investigated to deepen the understanding of bulk information for this compound. The valence band spectra of HAXPES presented the main contribution from Ga 4sp, which are well represented by photoionization cross section weighted partial density of states. The experimental data complemented with the theoretical study yield a realistic picture of the electronic structure for β-Ga{sub 2}O{sub 3}.

  2. Coherent control of photoelectron wavepacket angular interferograms

    NASA Astrophysics Data System (ADS)

    Hockett, P.; Wollenhaupt, M.; Baumert, T.

    2015-11-01

    Coherent control over photoelectron wavepackets, via the use of polarization-shaped laser pulses, can be understood as a time and polarization-multiplexed process, where the final (time-integrated) observable coherently samples all instantaneous states of the light-matter interaction. In this work, we investigate this multiplexing via computation of the observable photoelectron angular interferograms resulting from multi-photon atomic ionization with polarization-shaped laser pulses. We consider the polarization sensitivity of both the instantaneous and cumulative continuum wavefunction; the nature of the coherent control over the resultant photoelectron interferogram is thus explored in detail. Based on this understanding, the use of coherent control with polarization-shaped pulses as a methodology for a highly multiplexed coherent quantum metrology is also investigated, and defined in terms of the information content of the observable.

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

    NASA Astrophysics Data System (ADS)

    Habibi, Mustapha

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

  4. Photoionization of ground and excited levels of P II

    NASA Astrophysics Data System (ADS)

    Nahar, Sultana N.

    2017-01-01

    Photoionization cross section (σPI) of P II, (hν + P II → P III + e), from ground and a large number of excited levels are presented. The study includes the resonant structures and the characteristics of the background in photoionization cross sections. The present calculations were carried out in the Breit-Pauli R-matrix (BPRM) method that includes relativistic effects. The autoionizing resonances are delineated with a fine energy mesh to observe the fine structure effects. A singular resonance, formed by the coupling of channels in fine structure but not allowed in LS coupling, is seen at the ionization threshold of photoionization for the ground and many excited levels. The background cross section is seen enhanced compared to smooth decay for the excited levels. Examples are presented to illustrate the enhanced background cross sections at the energies of the core levels, 4P3/2 and 2D3/2, that are allowed for electric dipole transitions by the core ground level 2 P1/2o. In addition strong Seaton or photo-excitation-of-core (PEC) resonances are found in the photoionization of single valence electron excited levels. Calculations used a close coupling wave function expansion that included 18 fine structure levels of core P III from configurations 3s23p, 3s3p2, 3s23d, 3s24s, 3s24p and 3p3. Photoionization cross sections are presented for all 475 fine structure levels of P II found with n ≤ 10 and l ≤ 9. The present results will provide high precision parameters of various applications involving this less studied ion.

  5. Acid generation efficiency: EUV photons versus photoelectrons

    NASA Astrophysics Data System (ADS)

    Goldfarb, Dario L.; Afzali-Ardakani, Ali; Glodde, Martin

    2016-03-01

    EUV photoacid generation efficiency has been described primarily in terms of the EUV photon absorption by the PAG or the resist matrix and the production of low energy photoelectrons, which are reported as being ultimately responsible for the high quantum efficiencies reported in EUV resists (<1). Such observation led to a number of recent studies on PAGs with variable electron affinity (EA) and reduction potential (Ered) presumably conducive to a differential EUV photoelectron harvesting efficiency. However, such studies either did not disclose the PAG chemical structures, replaced the EUV source with an e-beam source, or lacked a fundamental discussion of the underlying physical mechanisms behind EUV PAG decomposition. In this work, we report the EUV photospeed of a methacrylatebased resist formulated with a battery of openly disclosed isostructural sulfonium PAGs covering a wide range of EA's and Ered's, to unveil any preferential photoelectron scavenging effect. In parallel, several iodonium PAGs are also tested in order to compare the direct EUV photon absorption route to the photoelectron-based decomposition path. Contrarily to what has been widely reported, we have found no direct correlation whatsoever between photospeed and the calculated EA's or experimental Ered's for the isostructural sulfonium PAGs studied. Instead, we found that iodonium PAGs make more efficient use of the available EUV power due to their higher photoabsorption cross-section. Additionally, we determined a cation size effect for both PAG groups, which is able to further modulate the acid generation efficiency. Finally, we present a formal explanation for the unselective response towards photoelectron harvesting based on the stabilization of the PAG cation by bulky substituent groups, the spatial and temporal range of the transient photoelectron and the differences in electron transfer processes for the different systems studied.

  6. A generalized model for coincidence counting

    SciTech Connect

    Lu, Ming-Shih; Teichmann, T.

    1993-12-31

    A generalized model for coincidence counting has been developed based on the dual probability generating function introduced. The model accounts explicitly and simultaneously the effects of multiplication, absorption by poison and instrument detection and is applicable for a wide class of NDA including Pu in waste.

  7. Spin-orbit-induced photoelectron spin polarization in angle-resolved photoemission from both atomic and condensed matter targets.

    PubMed

    Heinzmann, Ulrich; Dil, J Hugo

    2012-05-02

    The existence of highly spin polarized photoelectrons emitted from non-magnetic solids as well as from unpolarized atoms and molecules has been found to be very common in many studies over the past 40 years. This so-called Fano effect is based upon the influence of the spin-orbit interaction in the photoionization or the photoemission process. In a non-angle-resolved photoemission experiment, circularly polarized radiation has to be used to create spin polarized photoelectrons, while in angle-resolved photoemission even unpolarized or linearly polarized radiation is sufficient to get a high spin polarization. In past years the Rashba effect has become very important in the angle-resolved photoemission of solid surfaces, also with an observed high photoelectron spin polarization. It is the purpose of the present topical review to cross-compare the spin polarization experimentally found in angle-resolved photoelectron emission spectroscopy of condensed matter with that of free atoms, to compare it with the Rashba effect and topological insulators to describe the influence and the importance of the spin-orbit interaction and to show and disentangle the matrix element and phase shift effects therein.The relationship between the energy dispersion of these phase shifts and the emission delay of photoelectron emission in attosecond-resolved photoemission is also discussed. Furthermore the influence of chiral structures of the photo-effect target on the spin polarization, the interferences of different spin components in coherent superpositions in photoemission and a cross-comparison of spin polarization in photoemission from non-magnetic solids with XMCD on magnetic materials are presented; these are all based upon the influence of the spin-orbit interaction in angle-resolved photoemission.

  8. Photon momentum sharing between an electron and an ion in photoionization: from one-photon (photoelectric effect) to multiphoton absorption.

    PubMed

    Chelkowski, Szczepan; Bandrauk, André D; Corkum, Paul B

    2014-12-31

    We investigate photon-momentum sharing between an electron and an ion following different photoionization regimes. We find very different partitioning of the photon momentum in one-photon ionization (the photoelectric effect) as compared to multiphoton processes. In the photoelectric effect, the electron acquires a momentum that is much greater than the single photon momentum ℏω/c [up to (8/5) ℏω/c] whereas in the strong-field ionization regime, the photoelectron only acquires the momentum corresponding to the photons absorbed above the field-free ionization threshold plus a momentum corresponding to a fraction (3/10) of the ionization potential Ip. In both cases, due to the smallness of the electron-ion mass ratio, the ion takes nearly the entire momentum of all absorbed N photons (via the electron-ion center of mass). Additionally, the ion takes, as a recoil, the photoelectron momentum resulting from mutual electron-ion interaction in the electromagnetic field. Consequently, the momentum partitioning of the photofragments is very different in both regimes. This suggests that there is a rich, unexplored physics to be studied between these two limits which can be generated with current ultrafast laser technology.

  9. Photoelectron spectroscopy of nitromethane anion clusters

    NASA Astrophysics Data System (ADS)

    Pruitt, Carrie Jo M.; Albury, Rachael M.; Goebbert, Daniel J.

    2016-08-01

    Nitromethane anion and nitromethane dimer, trimer, and hydrated cluster anions were studied by photoelectron spectroscopy. Vertical detachment energies, estimated electron affinities, and solvation energies were obtained from the photoelectron spectra. Cluster structures were investigated using theoretical calculations. Predicted detachment energies agreed with experiment. Calculations show water binds to nitromethane anion through two hydrogen bonds. The dimer has a non-linear structure with a single ionic Csbnd H⋯O hydrogen bond. The trimer has two different solvent interactions, but both involve the weak Csbnd H⋯O hydrogen bond.

  10. Anion photoelectron imaging spectroscopy of glyoxal

    NASA Astrophysics Data System (ADS)

    Xue, Tian; Dixon, Andrew R.; Sanov, Andrei

    2016-09-01

    We report a photoelectron imaging study of the radical-anion of glyoxal. The 532 nm photoelectron spectrum provides the first direct spectroscopic determination of the adiabatic electron affinity of glyoxal, EA = 1.10 ± 0.02 eV. This assignment is supported by a Franck-Condon simulation of the experimental spectrum that successfully reproduces the observed spectral features. The vertical detachment energy of the radical-anion is determined as VDE = 1.30 ± 0.04 eV. The reported EA and VDE values are attributed to the most stable (C2h symmetry) isomers of the neutral and the anion.

  11. Photoelectron Emission Spectroscopy of Liquid Water.

    DTIC Science & Technology

    1981-04-01

    correlated to solvation free energies for H2O+(aq) and OH (aq)., DD ,FO*M 1473 EDITIOOF INOV so iS OBSOLETE Unclassified SECURITY CLASSIFICATION OF THIS PAGE...Photoelectron spectroscopy Reorganization free energy Water, liquid 20. ABSTRACT (Chlnw am ef We, aid* it nooe"mr and 1iEru’h hr 190k le 6) The threshold... energy Et a 10.06 eV (0.002 @V standard deviation) is detemined for phot~oelectron emission by litquid water and is correlated with Et a 8.45 eV for

  12. Spin polarization of photoelectrons from topological insulators.

    PubMed

    Park, Cheol-Hwan; Louie, Steven G

    2012-08-31

    We show that the degree of spin polarization of photoelectrons from the surface states of topological insulators is 100% if fully polarized light is used as in typical photoemission measurements, and, hence, can be significantly higher than that of the initial state. Further, the spin orientation of these photoelectrons in general can also be very different from that of the initial surface state and is controlled by the photon polarization. A rich set of predicted phenomena have recently been confirmed by spin- and angle-resolved photoemission experiments.

  13. Observation of spin-polarized photoelectron diffraction

    NASA Astrophysics Data System (ADS)

    Sinković, B.; Hermsmeier, B.; Fadley, C. S.

    1985-09-01

    We report the first observation of spin-polarized photoelectron diffraction in core-level emission from anti-ferromagnetic KMnF3. The Mn 3s multiplet splitting provides an internal source of polarized electrons, and spin polarized photoelectron diffraction effects of up to 17% are seen in the 5/ 7S intensity ratio. These effects are found to be very sensitive to both emission direction and temperature. Short-range antiferromagnetic order is found to persist up to approximately three times the Neél temperature.

  14. Using Compton scattering for random coincidence rejection

    NASA Astrophysics Data System (ADS)

    Kolstein, M.; Chmeissani, M.

    2016-12-01

    The Voxel Imaging PET (VIP) project presents a new approach for the design of nuclear medicine imaging devices by using highly segmented pixel CdTe sensors. CdTe detectors can achieve an energy resolution of ≈ 1% FWHM at 511 keV and can be easily segmented into submillimeter sized voxels for optimal spatial resolution. These features help in rejecting a large part of the scattered events from the PET coincidence sample in order to obtain high quality images. Another contribution to the background are random events, i.e., hits caused by two independent gammas without a common origin. Given that 60% of 511 keV photons undergo Compton scattering in CdTe (i.e. 84% of all coincidence events have at least one Compton scattering gamma), we present a simulation study on the possibility to use the Compton scattering information of at least one of the coincident gammas within the detector to reject random coincidences. The idea uses the fact that if a gamma undergoes Compton scattering in the detector, it will cause two hits in the pixel detectors. The first hit corresponds to the Compton scattering process. The second hit shall correspond to the photoelectric absorption of the remaining energy of the gamma. With the energy deposition of the first hit, one can calculate the Compton scattering angle. By measuring the hit location of the coincident gamma, we can construct the geometric angle, under the assumption that both gammas come from the same origin. Using the difference between the Compton scattering angle and the geometric angle, random events can be rejected.

  15. Coincidence velocity map imaging using a single detector

    NASA Astrophysics Data System (ADS)

    Zhao, Arthur; Sándor, Péter; Weinacht, Thomas

    2017-07-01

    We demonstrate a single-detector velocity map imaging setup which is capable of rapidly switching between coincidence and non-coincidence measurements. By rapidly switching the extraction voltages on the electrostatic lenses, both electrons and ions can be collected in coincidence with a single detector. Using a fast camera as the 2D detector avoids the saturation problem associated with traditional delay line detectors and allows for easy transitions between coincidence and non-coincidence data collection modes. This is a major advantage in setting up a low-cost and versatile coincidence apparatus. We present both coincidence and non-coincidence measurements of strong field atomic and molecular ionization.

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

    NASA Astrophysics Data System (ADS)

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

    1997-08-01

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

  17. Imaging molecules from within: Ultrafast angstroem-scale structure determination of molecules via photoelectron holography using free-electron lasers

    SciTech Connect

    Krasniqi, F.; Rolles, D.; Najjari, B.; Voitkiv, A.; Strueder, L.; Ullrich, J.

    2010-03-15

    A scheme based on (i) upcoming brilliant x-ray free-electron laser (FEL) sources, (ii) innovative energy and angular-dispersive large-area electron imagers, and (iii) the well-known photoelectron holography is elaborated that provides time-dependent three-dimensional structure determination of small to medium-sized molecules with Angstroem spatial and femtosecond time resolution. Inducing molecular dynamics, wave-packet motion, dissociation, passage through conical intersections, or isomerization by a pump pulse this motion is visualized by the x-ray FEL probe pulse launching keV photoelectrons within a few femtoseconds from specific and well-defined sites, deep core levels of individual atoms, inside the molecule. On their way out, the photoelectrons are diffracted generating a hologram on the detector that encodes the molecular structure at the instant of photoionization, thus providing 'femtosecond snapshot images of the molecule from within'. Detailed calculations in various approximations of increasing sophistication are presented and three-dimensional retrieval of the spatial structure of the molecule with Angstroem spatial resolution is demonstrated. Due to the large photoabsorption cross sections the method extends x-ray-diffraction-based time-dependent structure investigations envisioned at FEL's to new classes of samples that are not accessible by any other method. Among them are dilute samples in the gas phase such as aligned, oriented, or conformer-selected molecules, ultracold ensembles and/or molecular or cluster objects containing mainly light atoms that do not scatter x rays efficiently.

  18. VUV photoionization and dissociative photoionization of the prebiotic molecule acetyl cyanide: Theory and experiment

    SciTech Connect

    Bellili, A.; Hochlaf, M. E-mail: martin.schwell@lisa.u-pec.fr; Schwell, M. E-mail: martin.schwell@lisa.u-pec.fr; Bénilan, Y.; Fray, N.; Gazeau, M.-C.; Mogren Al-Mogren, M.; Guillemin, J.-C.; Poisson, L.

    2014-10-07

    The present combined theoretical and experimental investigation concerns the single photoionization of gas-phase acetyl cyanide and the fragmentation pathways of the resulting cation. Acetyl cyanide (AC) is inspired from both the chemistry of cyanoacetylene and the Strecker reaction which are thought to be at the origin of medium sized prebiotic molecules in the interstellar medium. AC can be formed by reaction from cyanoacetylene and water but also from acetaldehyde and HCN or the corresponding radicals. In view of the interpretation of vacuum ultraviolet (VUV) experimental data obtained using synchrotron radiation, we explored the ground potential energy surface (PES) of acetyl cyanide and of its cation using standard and recently implemented explicitly correlated methodologies. Our PES covers the regions of tautomerism (between keto and enol forms) and of the lowest fragmentation channels. This allowed us to deduce accurate thermochemical data for this astrobiologically relevant molecule. Unimolecular decomposition of the AC cation turns out to be very complex. The implications for the evolution of prebiotic molecules under VUV irradiation are discussed.

  19. VUV photoionization and dissociative photoionization of the prebiotic molecule acetyl cyanide: Theory and experiment

    NASA Astrophysics Data System (ADS)

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

    2014-10-01

    The present combined theoretical and experimental investigation concerns the single photoionization of gas-phase acetyl cyanide and the fragmentation pathways of the resulting cation. Acetyl cyanide (AC) is inspired from both the chemistry of cyanoacetylene and the Strecker reaction which are thought to be at the origin of medium sized prebiotic molecules in the interstellar medium. AC can be formed by reaction from cyanoacetylene and water but also from acetaldehyde and HCN or the corresponding radicals. In view of the interpretation of vacuum ultraviolet (VUV) experimental data obtained using synchrotron radiation, we explored the ground potential energy surface (PES) of acetyl cyanide and of its cation using standard and recently implemented explicitly correlated methodologies. Our PES covers the regions of tautomerism (between keto and enol forms) and of the lowest fragmentation channels. This allowed us to deduce accurate thermochemical data for this astrobiologically relevant molecule. Unimolecular decomposition of the AC cation turns out to be very complex. The implications for the evolution of prebiotic molecules under VUV irradiation are discussed.

  20. Enormous yield of photoelectrons from small particles

    NASA Astrophysics Data System (ADS)

    Schmidt-Ott, A.; Schurtenberger, P.; Siegmann, H. C.

    1980-10-01

    The paper reports a large enhancement of the yield of photoelectrons per incident photon if ultrafine particles with radii not greater than 50 A are chosen as photoemitters. The results are obtained with Ag and WO3 by the use of an ac bridge technique making it possible to study very small particles suspended in gases.

  1. Photoelectron Spectroscopy in Advanced Placement Chemistry

    ERIC Educational Resources Information Center

    Benigna, James

    2014-01-01

    Photoelectron spectroscopy (PES) is a new addition to the Advanced Placement (AP) Chemistry curriculum. This article explains the rationale for its inclusion, an overview of how the PES instrument records data, how the data can be analyzed, and how to include PES data in the course. Sample assessment items and analysis are included, as well as…

  2. Instrumentation for the Atmospheric Explorer photoelectron spectrometer

    NASA Technical Reports Server (NTRS)

    Peletier, D. P.

    1973-01-01

    The photoelectron spectrometer (PES) is part of the complements of scientific instruments aboard three NASA Atmosphere Explorer (AE) satellites. The PES measures the energy spectrum, angular distribution, and intensity of electrons in the earth's thermosphere. Measurements of energies between 2 and 500 eV are made at altitudes as low as 130 km. The design, characteristics, and performance of the instrument are described.

  3. Photoelectron Spectroscopy in Advanced Placement Chemistry

    ERIC Educational Resources Information Center

    Benigna, James

    2014-01-01

    Photoelectron spectroscopy (PES) is a new addition to the Advanced Placement (AP) Chemistry curriculum. This article explains the rationale for its inclusion, an overview of how the PES instrument records data, how the data can be analyzed, and how to include PES data in the course. Sample assessment items and analysis are included, as well as…

  4. Photoelectron spectroscopy and the dipole approximation

    SciTech Connect

    Hemmers, O.; Hansen, D.L.; Wang, H.

    1997-04-01

    Photoelectron spectroscopy is a powerful technique because it directly probes, via the measurement of photoelectron kinetic energies, orbital and band structure in valence and core levels in a wide variety of samples. The technique becomes even more powerful when it is performed in an angle-resolved mode, where photoelectrons are distinguished not only by their kinetic energy, but by their direction of emission as well. Determining the probability of electron ejection as a function of angle probes the different quantum-mechanical channels available to a photoemission process, because it is sensitive to phase differences among the channels. As a result, angle-resolved photoemission has been used successfully for many years to provide stringent tests of the understanding of basic physical processes underlying gas-phase and solid-state interactions with radiation. One mainstay in the application of angle-resolved photoelectron spectroscopy is the well-known electric-dipole approximation for photon interactions. In this simplification, all higher-order terms, such as those due to electric-quadrupole and magnetic-dipole interactions, are neglected. As the photon energy increases, however, effects beyond the dipole approximation become important. To best determine the range of validity of the dipole approximation, photoemission measurements on a simple atomic system, neon, where extra-atomic effects cannot play a role, were performed at BL 8.0. The measurements show that deviations from {open_quotes}dipole{close_quotes} expectations in angle-resolved valence photoemission are observable for photon energies down to at least 0.25 keV, and are quite significant at energies around 1 keV. From these results, it is clear that non-dipole angular-distribution effects may need to be considered in any application of angle-resolved photoelectron spectroscopy that uses x-ray photons of energies as low as a few hundred eV.

  5. Toward a solution of the coincidence problem

    SciTech Connect

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

    2008-07-15

    The coincidence problem of late cosmic acceleration constitutes a serious riddle with regard to our understanding of the evolution of the Universe. Here we argue that this problem may someday be solved - or better understood - by expressing the Hubble expansion rate as a function of the ratio of densities (dark matter/dark energy) and observationally determining the said rate in terms of the redshift.

  6. Fast coincidence counting with active inspection systems

    NASA Astrophysics Data System (ADS)

    Mullens, J. A.; Neal, J. S.; Hausladen, P. A.; Pozzi, S. A.; Mihalczo, J. T.

    2005-12-01

    This paper describes 2nd and 3rd order time coincidence distributions measurements with a GHz processor that synchronously samples 5 or 10 channels of data from radiation detectors near fissile material. On-line, time coincidence distributions are measured between detectors or between detectors and an external stimulating source. Detector-to-detector correlations are useful for passive measurements also. The processor also measures the number of times n pulses occur in a selectable time window and compares this multiplet distribution to a Poisson distribution as a method of determining the occurrence of fission. The detectors respond to radiation emitted in the fission process induced internally by inherent sources or by external sources such as LINACS, DT generators either pulsed or steady state with alpha detectors, etc. Data can be acquired from prompt emission during the source pulse, prompt emissions immediately after the source pulse, or delayed emissions between source pulses. These types of time coincidence measurements (occurring on the time scale of the fission chain multiplication processes for nuclear weapons grade U and Pu) are useful for determining the presence of these fissile materials and quantifying the amount, and are useful for counter terrorism and nuclear material control and accountability. This paper presents the results for a variety of measurements.

  7. Experimental and Computational Investigations of the Threshold Photoelectron Spectrum of the HCCN Radical

    NASA Astrophysics Data System (ADS)

    Gans, B.; Falvo, Cyril; Coudert, L. H.; Garcia, Gustavo A.; Küger, J.; Loison, J.-C.

    2017-06-01

    The HCCN radical, already detected in the interstellar medium, is also important for nitrile chemistry in Titan's atmosphere. Quite recently the photoionization spectrum of the radical has been recorded using mass selected threshold photoelectron (TPE) spectroscopy and this provided us with the first spectroscopic information about the HCCN} cation. Modeling such a spectrum requires accounting for the non-rigidity of HCCN and for the Renner-Teller effect in HCCN+. In its ^3A'' electronic ground state, HCCN is a non-rigid molecule as the potential for the \\angle{HCC} bending angle is very shallow. Vibronic couplings with the same bending angle leads, in the ^2Π electronic ground state of HCCN+, to a strong Renner-Teller effect giving rise to a bent ^2A' and a quasi-linear ^2A'' state. In this paper the photoionization spectrum of the HCCN radical is simulated. The model developped treats the \\angle{HCC} bending angle as a large amplitude coordinate in both the radical and the cation and accounts for the overall rotation and the Renner-Teller couplings. Gaussian quadrature are used to calculate matrix elements of the three potential energy functions retrieved through ab initio calculations and rovibrational operators going to infinity for the linear configuration are treated rigorously. The HCCN TPE spectrum is computed with the above model calculating all rotational components and choosing the appropriate lineshape. This synthetic spectrum will be shown in the paper and compared with the experimental one.^b Guélin and Cernicharo, A&A 244 (1991) L21 Loison et al., Icarus 247 (2015) 218 Garcia, Krüger, Gans, Falvo, Coudert, and Loison, J. Chem. Phys. (2017) submitted Koput, J. Phys. Chem. A 106 (2002) 6183 Zhao, Zhang, and Sun, J. Phys. Chem. A 112 (2008) 12125

  8. Time-Dependent Photoionization of Gas Outflows in AGN

    NASA Astrophysics Data System (ADS)

    Elhoussieny, Ehab E.; Bautista, M.; Garcia, J.; Kallman, T. R.

    2013-01-01

    Gas outflows are fundamental components of Active Galactic Nuclei (AGN) activity. Time-variability of ionizing radiation, which is characteristic of AGN in various different time scales, may produce non-equilibrium photoionization conditions over a significant fraction of the flow and yields supersonically moving cooling/heating fronts. These fast fronts create pressure imbalances that can only be resolved by fragmentation of the flow and acceleration of such fragments. This mechanism can explain the kinematic structure of low ionization BAL systems (FeLoBAL). This mechanism may also have significant effects on other types of outflows given the wide range of variability time scales in AGN. We will study these effects in detail by constructing time-dependent photoionization models of the outflows and incorporating these models into radiative-hydrodynamic simulations.

  9. K -shell double photoionization of Be, Mg, and Ca

    NASA Astrophysics Data System (ADS)

    Kheifets, A. S.; Bray, Igor; Hoszowska, J.

    2009-04-01

    We perform convergent close-coupling calculations of double photoionization (DPI) of the K -shell of alkaline-earth metal atoms (Be, Mg, and Ca) from the threshold to the nonrelativistic limit of infinite photon energy. Theoretical double-to-single photoionization cross-section ratios for Mg and Ca are compared with experimental values derived from high-resolution x-ray spectra following the radiative decay of the K -shell double vacancy. We investigate the role of many-electron correlations in the ground and doubly-ionized final states played in the DPI process. Universal scaling of DPI cross section with an effective nuclear charge is examined in neutral atoms in comparison with corresponding heliumlike ions.

  10. Vibrationally resolved shape resonant photoionization of SiF4

    NASA Astrophysics Data System (ADS)

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

    1992-01-01

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

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

    NASA Astrophysics Data System (ADS)

    Poliakoff, Erwin D.

    1988-11-01

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

  12. Spatially resolved photoionization of ultracold atoms on an atom chip

    SciTech Connect

    Kraft, S.; Guenther, A.; Fortagh, J.; Zimmermann, C.

    2007-06-15

    We report on photoionization of ultracold magnetically trapped Rb atoms on an atom chip. The atoms are trapped at 5 {mu}K in a strongly anisotropic trap. Through a hole in the chip with a diameter of 150 {mu}m, two laser beams are focused onto a fraction of the atomic cloud. A first laser beam with a wavelength of 778 nm excites the atoms via a two-photon transition to the 5D level. With a fiber laser at 1080 nm the excited atoms are photoionized. Ionization leads to depletion of the atomic density distribution observed by absorption imaging. The resonant ionization spectrum is reported. The setup used in this experiment is suitable not only to investigate mixtures of Bose-Einstein condensates and ions but also for single-atom detection on an atom chip.

  13. Double-photoionization of helium including quadrupole radiation effects

    SciTech Connect

    Colgan, James; Ludlow, J A; Lee, Teck - Ghee; Pindzola, M S; Robicheaux, F

    2009-01-01

    Non-perturbative time-dependent close-coupling calculations are carried out for the double photoionization of helium including both dipole and quadrupole radiation effects. At a photon energy of 800 eV, accessible at CUlTent synchrotron light sources, the quadrupole interaction contributes around 6% to the total integral double photoionization cross section. The pure quadrupole single energy differential cross section shows a local maxima at equal energy sharing, as opposed to the minimum found in the pure dipole single energy differential cross section. The sum of the pure dipole and pure quadrupole single energy differentials is insensitive to non-dipole effects at 800 eV. However, the triple differential cross section at equal energy sharing of the two ejected electrons shows strong non-dipole effects due to the quadrupole interaction that may be experimentally observable.

  14. A smog chamber study coupling a photoionization aerosol electron/ion spectrometer to VUV synchrotron radiation: organic and inorganic-organic mixed aerosol analysis

    NASA Astrophysics Data System (ADS)

    Baeza-Romero, María Teresa; Gaie-Levrel, Francois; Mahjoub, Ahmed; López-Arza, Vicente; Garcia, Gustavo A.; Nahon, Laurent

    2016-07-01

    A reaction chamber was coupled to a photoionization aerosol time-of-flight mass spectrometer based on an electron/ion coincidence scheme and applied for on-line analysis of organic and inorganic-organic mixed aerosols using synchrotron tunable vacuum ultraviolet (VUV) photons as the ionization source. In this proof of principle study, both aerosol and gas phase were detected simultaneously but could be differentiated. Present results and perspectives for improvement for this set-up are shown in the study of ozonolysis ([O3] = 0.13-3 ppm) of α-pinene (2-3 ppm), and the uptake of glyoxal upon ammonium sulphate. In this work the ozone concentration was monitored in real time, together with the particle size distributions and chemical composition, the latter taking advantage of the coincidence spectrometer and the tuneability of the synchrotron radiation as a soft VUV ionization source.

  15. Nonperturbative theory of double photoionization of the hydrogen molecule

    SciTech Connect

    Vanroose, W.; Martin, F.; Rescigno, T.N.; McCurdy, C.W.

    2004-10-01

    We present completely ab initio nonperturbative calculations of the integral and single differential cross sections for double photoionization of H2 for photon energies from 53.9 to 75.7 eV. The method of exterior complex scaling, implemented with B-splines, is used to solve the Schrodinger equation for a correlated continuum wave function corresponding to a single photon having been absorbed by a correlated initial state. The results are in good agreement with experimental integral cross sections.

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

    NASA Astrophysics Data System (ADS)

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

    2012-11-01

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

  17. Differential cross sections of double photoionization of lithium

    SciTech Connect

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

    2010-08-15

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

  18. Tunable Wavelength Soft Photoionization of Ionic Liquid Vapors (Preprint)

    DTIC Science & Technology

    2009-11-18

    determined using the atomic absorption line spectrum of an argon gas filter located between the light Preprint Distribution A: Approved for public...Journal of the American Society for Mass Spectrometry; 19, 1347 (2008). 28. P.B. Corkum, Plasma Perspective on Strong-Field Multiphoton Ionization...Physical Review Letters; 71, 1994 (1993). 29. L. Belau et al., Vacuum ultraviolet ( VUV ) photoionization of small water clusters. Journal of

  19. Photoionization of an aluminum plasma by a tantalum X source

    NASA Astrophysics Data System (ADS)

    Renaudin, Patrick; Back, Christina A.; Chenais-Popovics, Claude; Audebert, Patrick; Geindre, Jean-Paul; Gauthier, Jean-Claude

    1991-05-01

    Photoionization of a helium like aliminum plasma is carried out by an external x-source. The laser beam used corresponds to the 3d to 4F transition level of tantalum. The experimental spectrum of tantalum is shown superimposed over the emission spectrum of aluminum on diagrammatic form. Good correspondence is seen between the 3d to 4F emissions of tantalum and helium like aluminum. Plasma pumping is obtained by exposure of a tantalum target to laser rays.

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

    NASA Astrophysics Data System (ADS)

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

    1992-11-01

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

  1. Precision measurements on the photoionization of neutral atomic species

    NASA Astrophysics Data System (ADS)

    Stolte, Wayne

    2016-05-01

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

  2. Photoionization sensors for non-invasive medical diagnostics

    NASA Astrophysics Data System (ADS)

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

    2016-09-01

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

  3. Photoionization Modeling and the K Lines of Iron

    NASA Technical Reports Server (NTRS)

    Kallman, T. R.; Palmeri, P.; Bautista, M. A.; Mendoza, C.; Krolik, J. H.

    2004-01-01

    We calculate the efficiency of iron K line emission and iron K absorption in photoionized models using a new set of atomic data. These data are more comprehensive than those previously applied to the modeling of iron K lines from photoionized gases, and allow us to systematically examine the behavior of the properties of line emission and absorption as a function of the ionization parameter, density and column density of model constant density clouds. We show that, for example, the net fluorescence yield for the highly charged ions is sensitive to the level population distribution produced by photoionization, and these yields are generally smaller than those predicted assuming the population is according to statistical weight. We demonstrate that the effects of the many strongly damped resonances below the K ionization thresholds conspire to smear the edge, thereby potentially affecting the astrophysical interpretation of absorption features in the 7-9 keV energy band. We show that the centroid of the ensemble of K(alpha) lines, the K(beta) energy, and the ratio of the K(alpha(sub 1)) to K(alpha(sub 2)) components are all diagnostics of the ionization parameter of our model slabs.

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

    NASA Astrophysics Data System (ADS)

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

    2015-02-01

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

  5. 2s photoionization and subsequent Auger cascade in atomic Si

    SciTech Connect

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

    2010-06-15

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

  6. Solvent jet desorption capillary photoionization-mass spectrometry.

    PubMed

    Haapala, Markus; Teppo, Jaakko; Ollikainen, Elisa; Kiiski, Iiro; Vaikkinen, Anu; Kauppila, Tiina J; Kostiainen, Risto

    2015-03-17

    A new ambient mass spectrometry method, solvent jet desorption capillary photoionization (DCPI), is described. The method uses a solvent jet generated by a coaxial nebulizer operated at ambient conditions with nitrogen as nebulizer gas. The solvent jet is directed onto a sample surface, from which analytes are extracted into the solvent and ejected from the surface in secondary droplets formed in collisions between the jet and the sample surface. The secondary droplets are directed into the heated capillary photoionization (CPI) device, where the droplets are vaporized and the gaseous analytes are ionized by 10 eV photons generated by a vacuum ultraviolet (VUV) krypton discharge lamp. As the CPI device is directly connected to the extended capillary inlet of the MS, high ion transfer efficiency to the vacuum of MS is achieved. The solvent jet DCPI provides several advantages: high sensitivity for nonpolar and polar compounds with limit of detection down to low fmol levels, capability of analyzing small and large molecules, and good spatial resolution (250 μm). Two ionization mechanisms are involved in DCPI: atmospheric pressure photoionization, capable of ionizing polar and nonpolar compounds, and solvent assisted inlet ionization capable of ionizing larger molecules like peptides. The feasibility of DCPI was successfully tested in the analysis of polar and nonpolar compounds in sage leaves and chili pepper.

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

    PubMed

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

    2007-10-11

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

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

    NASA Astrophysics Data System (ADS)

    Frazer, Nicholas Laszlo

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

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

    PubMed

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

    2015-02-26

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

  10. Femtosecond pump-probe photoionization-photofragmentation spectroscopy: Photoionization-induced twisting and coherent vibrational motion of azobenzene cation

    NASA Astrophysics Data System (ADS)

    Ho-Wei, Jr.; Chen, Wei-Kan; Cheng, Po-Yuan

    2009-10-01

    We report studies of ultrafast dynamics of azobenzene cation using femtosecond photoionization-photofragmentation spectroscopy. In our experiments, a femtosecond pump pulse first produces an ensemble of azobenzene cations via photoionization of the neutrals. A delayed probe pulse then brings the evolving ionic system to excited states that ultimately undergo ion fragmentation. The dynamics is followed by monitoring either the parent-ion depletion or fragment-ion formation as a function of the pump-probe delay time. The observed transients for azobenzene cation are characterized by a constant ion depletion modulated by a rapidly damped oscillatory signal with a period of about 1 ps. Theoretical calculations suggest that the oscillation arises from a vibration motion along the twisting inversion coordinate involving displacements in CNNC and phenyl-ring torsions. The oscillation is damped rapidly with a time constant of about 1.2 ps, suggesting that energy dissipation from the active mode to bath modes takes place in this time scale.

  11. Theory of photoelectron production, transport and energy loss

    NASA Technical Reports Server (NTRS)

    Nagy, A. F.

    1974-01-01

    Current understanding of the theory of ionospheric photoelectron production, transport and energy loss is summarized. The various approaches used in the theoretical calculations of photoelectron fluxes appear to be self consistent and sound; improved values for a number of input parameters are needed now in order to achieve significant improvements and more confidence in the results. The major remaining problem in the present day theory of photoelectron transport and energy loss is centered around the calculations of photoelectron transit through the protonosphere.

  12. Photoelectron Spectroscopy for Identification of Chemical States

    NASA Technical Reports Server (NTRS)

    Novakov, T.

    1971-01-01

    The technique of X-ray photoelectron spectroscopy and the fundamental electronic interactions constituting the basis of the method will be discussed. The method provides information about chemical states ("oxidation states") of atoms in molecules. In addition, quantitative elemental analysis can be performed using the same method. On the basis of this information identification of chemical species is possible. Examples of applications are discussed with particular references to the study of smog particulate matter.

  13. On the Photoelectron Spectra of Li4

    NASA Technical Reports Server (NTRS)

    Bauschlicher, Charles W., Jr.; Arnold, James O. (Technical Monitor)

    1996-01-01

    The most stable structure for Li4(-) is found to be the rhombus. Electron detachment from this structure does not seem able to fully explain the photoelectron spectra. The computed results are consistent with those Rao, Jena, and Ray who have proposed that the experimental spectra consists of a superposition of detachment from the Li4(-) rhombus and tetrahedron, forming the singlet and triplet states of Li4, respectively.

  14. Photoionized Plasmas in the Z Facility and in Astrophysics

    NASA Astrophysics Data System (ADS)

    Mancini, Roberto

    2013-06-01

    Many astrophysical environments such as x-ray binaries, active galactic nuclei, and accretion disks of compact objects have photoionized plasmas. Detailed x-ray spectral observations performed with the Chandra and XMM-Newton orbiting telescopes provide critical information on the state of photoionized plasmas. However, the complexity of the astrophysical environment makes the spectral analysis challenging, and thus laboratory experiments are important for data interpretation and testing of modeling codes. The Z facility at Sandia National Laboratories is a powerful source of x-rays to produce and study in the laboratory photoionized plasmas relevant for astrophysics under well characterized conditions. We discuss an experimental and theory/modeling effort in which the intense x-ray flux emitted at the collapse of a z-pinch implosion conducted at the Z pulsed-power machine is employed to produce a neon photoionized plasma. The broadband x-ray radiation flux from the z-pinch is used to both create the photoionized plasma and provide a source of backlighting photons to study the atomic kinetics through K-shell line absorption spectroscopy. The plasma is contained in a cm-scale gas cell that can be located at different distances from the z-pinch, thus effectively controlling the x-ray flux producing the plasma. Time-integrated and gated transmission spectra are recorded with a spectrometer equipped with two elliptically-bent KAP crystals and a set of slits to record up to six spatially-resolved spectra per crystal in the same shot. The transmission data shows a rich line absorption spectrum that spans over several ionization stages of neon including Be-, Li-, He- and H-like ions. Modeling calculations are used to interpret the transmission spectra recorded in the Z experiments with the goal of extracting the charge- state distribution, electron temperature and the radiation flux driving the plasma, as well as to determine the ionization parameter of the plasma. This

  15. Cosmic Coincidences: Investigations for Neutron Background Suppression

    PubMed Central

    Heimbach, Craig R.

    2007-01-01

    Two experimental investigations were made in order to reduce background counts in neutron detectors. Each investigation relied upon the fact that neutron background is largely due to cosmic ray interactions with the air and ground. The first attempt was to look at neutron arrival times. Neutron events close in time were taken to have been of a common origin due to cosmic rays. The second investigation was similar, but based on coincident neutron/muon events. The investigations showed only a small effect, not practical for the suppression of neutron background. PMID:27110457

  16. Cosmic Coincidences: Investigations for Neutron Background Suppression.

    PubMed

    Heimbach, Craig R

    2007-01-01

    Two experimental investigations were made in order to reduce background counts in neutron detectors. Each investigation relied upon the fact that neutron background is largely due to cosmic ray interactions with the air and ground. The first attempt was to look at neutron arrival times. Neutron events close in time were taken to have been of a common origin due to cosmic rays. The second investigation was similar, but based on coincident neutron/muon events. The investigations showed only a small effect, not practical for the suppression of neutron background.

  17. A method for coincidence timing resolution enhancement

    SciTech Connect

    Ermis, E. E. Celiktas, C.; Pilicer, E.

    2016-05-15

    A method including the coincidence time resolution improvement for a TOF/positron emission tomography system was suggested. The spectrometer for this aim was composed of two NaI(Tl) and two plastic scintillation detectors. Experimental results were supported by FLUKA Monte Carlo simulation program by constructing the detector setup in software medium. Present experimental results verified our previous results and conclusions obtained from the suggested method. It was concluded that better resolutions would help the improvement not only on the TOF gain but also on the spatial resolution, leading to better images and helping the Physician in his/her diagnosis and treatment.

  18. Photoelectron Spectroscopy of U Oxide at LLNL

    SciTech Connect

    Tobin, J G; Yu, S; Chung, B W; Waddill, G D

    2010-03-02

    In our laboratory at LLNL, an effort is underway to investigate the underlying complexity of 5f electronic structure with spin-resolved photoelectron spectroscopy using chiral photonic excitation, i.e. Fano Spectroscopy. Our previous Fano measurements with Ce indicate the efficacy of this approach and theoretical calculations and spectral simulations suggest that Fano Spectroscopy may resolve the controversy concerning Pu electronic structure and electron correlation. To this end, we have constructed and commissioned a new Fano Spectrometer, testing it with the relativistic 5d system Pt. Here, our preliminary photoelectron spectra of the UO{sub 2} system are presented. X-ray photoelectron spectroscopy has been used to characterize a sample of UO{sub 2} grown on an underlying substrate of Uranium. Both AlK{alpha} (1487 eV) and MgK{alpha} (1254 eV) emission were utilized as the excitation. Using XPS and comparing to reference spectra, it has been shown that our sample is clearly UO{sub 2}.

  19. Anion photoelectron spectroscopy of radicals and clusters

    SciTech Connect

    Travis, Taylor R.

    1999-12-01

    Anion photoelectron spectroscopy is used to study free radicals and clusters. The low-lying 2Σ and 2π states of C2nH (n = 1--4) have been studied. The anion photoelectron spectra yielded electron affinities, term values, and vibrational frequencies for these combustion and astrophysically relevant species. Photoelectron angular distributions allowed the author to correctly assign the electronic symmetry of the ground and first excited states and to assess the degree of vibronic coupling in C2H and C4H. Other radicals studied include NCN and I3. The author was able to observe the low-lying singlet and triplet states of NCN for the first time. Measurement of the electron affinity of I3 revealed that it has a bound ground state and attachment of an argon atom to this moiety enabled him to resolve the symmetric stretching progression.

  20. X-ray Photoelectron Spectroscopy Database (Version 4.1)

    National Institute of Standards and Technology Data Gateway

    SRD 20 X-ray Photoelectron Spectroscopy Database (Version 4.1) (Web, free access)   The NIST XPS Database gives access to energies of many photoelectron and Auger-electron spectral lines. The database contains over 22,000 line positions, chemical shifts, doublet splittings, and energy separations of photoelectron and Auger-electron lines.