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Core-valence double photoionization of the CS2 molecule
Uppsala University, Disciplinary Domain of Science and Technology, Physics, Department of Physics and Astronomy, Soft X-Ray Physics.
Uppsala University, Disciplinary Domain of Science and Technology, Physics, Department of Physics and Astronomy, Soft X-Ray Physics.
Uppsala University, Disciplinary Domain of Science and Technology, Physics, Department of Physics and Astronomy, Soft X-Ray Physics.
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2010 (English)In: Journal of Chemical Physics, ISSN 0021-9606, E-ISSN 1089-7690, Vol. 133, no 9, p. 094305-Article in journal (Refereed) Published
Abstract [en]

Double photoionization spectra of the CS2 molecule have been recorded using the TOF-PEPECO technique in combination with synchrotron radiation at the photon energies h nu=220, 230, 240, 243, and 362.7 eV. The spectra were recorded in the S 2p and C 1s inner-shell ionization regions and reflect dicationic states formed out of one inner-shell vacancy and one vacancy in the valence region. MCSCF calculations were performed to model the energies of the dicationic states. The spectra associated with a S 2p vacancy are well structured and have been interpreted in some detail by comparison to conventional S 2p and valence photoelectron spectra. The lowest inner-shell-valence dicationic state is observed at the vertical double ionization energy 188.45 eV and is associated with a (2p(3/2))(-1)(2 pi(g))(-1) double vacancy. The spectrum connected to the C 1s vacancy shows a distinct line at 310.8 eV, accompanied by additional broad features at higher double ionization energies. This line is associated with a (C 1s)(-1)(2 pi(g))(-1) double vacancy.

Place, publisher, year, edition, pages
2010. Vol. 133, no 9, p. 094305-
Keywords [en]
carbon compounds, inner-shell ionisation, molecule-photon collisions, photoionisation, SCF calculations
National Category
Physical Sciences
Identifiers
URN: urn:nbn:se:uu:diva-122570DOI: 10.1063/1.3469812ISI: 000281742900011OAI: oai:DiVA.org:uu-122570DiVA, id: diva2:311088
Available from: 2010-04-20 Created: 2010-04-14 Last updated: 2017-12-12Bibliographically approved
In thesis
1. Multi-Electron Coincidence Studies of Atoms and Molecules
Open this publication in new window or tab >>Multi-Electron Coincidence Studies of Atoms and Molecules
2010 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

This thesis concerns multi-ionization coincidence measurements of atoms and small molecules using a magnetic bottle time-of-flight (TOF) spectrometer designed for multi-electron coincidence studies. Also, a time-of-flight mass spectrometer has been used together with the TOF electron  spectrometer for electron-ion coincidence measurements. The multi-ionization processes have been studied by employing a pulsed discharge lamp in the vacuum ultraviolet spectral region and synchrotron radiation in the soft X-ray region. The designs of the spectrometers are described in some detail, and several timing schemes suitable for the light sources mentioned above are presented.

Studies have been performed on krypton, molecular oxygen, carbon disulfide and a series of alcohol molecules. For the latter, double ionization spectra have been recorded and new information has been obtained on the dicationic states. A recently found rule-of-thumb  and quantum chemical calculations have been used to quantify the effective distance of the two vacancies in the dications of these molecules.

For Kr, O2, and CS2, single-photon core-valence spectra have been obtained at the synchrotron radiation facility BESSY II in Berlin and interpreted on the basis of quantum chemical calculations. These spectra show a remarkable similarity to conventional valence photoelectron spectra.

Spectra of triply charged ions were recorded, also at BESSY II, for Kr and CS2 by measuring, in coincidence, all three electrons ejected. The complex transition channels leading to tricationic states were mapped in substantial detail for Kr. It was found that for 3d-ionized krypton, the tricationic states are dominantly populated by cascade Auger decays via distinct intermediate states whose energies have been determined. The triple ionization spectra of CS2 from the direct double Auger effect via S2p, S2s and C1s hole states contain several resolved features and show selectivity based on the initial charge localisation and on the identity of the initial state.

Place, publisher, year, edition, pages
Uppsala: Acta Universitatis Upsaliensis, 2010. p. 71
Series
Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology, ISSN 1651-6214 ; 743
Keywords
multi-ionization, electron emission, time-of-flight spectroscopy, coincidence spectroscopy, core-valence ionization, synchrotron radiation, electron correlation
National Category
Atom and Molecular Physics and Optics
Research subject
Physics with spec. in Atomic, Molecular and Condensed Matter Physics
Identifiers
urn:nbn:se:uu:diva-122811 (URN)978-91-554-7805-6 (ISBN)
Public defence
2010-05-29, Häggsalen, Ångströmlaboratoriet, Lägerhyddsvägen 1, Uppsala, 13:15 (English)
Opponent
Supervisors
Available from: 2010-05-03 Created: 2010-04-20 Last updated: 2013-09-20
2. Studies of Single and Multiple Ionization Processes in Rare Gases and some Small Molecules
Open this publication in new window or tab >>Studies of Single and Multiple Ionization Processes in Rare Gases and some Small Molecules
2014 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

In this thesis various aspects of photoionization are investigated with respect to both single and multiple electron emission from atoms and molecules. The studies include both valence and core levels and involve transitions which leave the atoms or molecules in various charge states.

S2p electrons in the CS2 molecule were excited into Rydberg orbitals close to the ionization threshold. Subsequent autoionization leads to the emission of single electrons which were detected by a conventional electron spectrometer, bringing the molecule into various cationic states characterized by two valence holes and a Rydberg spectator electron. Vibrational progressions have been assigned as excitations of the totally symmetric v1 and the asymmetric stretching v3 modes in the cationic states.

Double ionization spectra of the CS2 molecule were recorded in the S2p and C1s innershell ionization regions using a magnetic bottle many-electron coincidence spectrometer, revealing dicationic states formed out of one inner-shell vacancy and one vacancy in the valence region. The spectrum connected to the S2p vacancy is richly structured in contrast to the spectrum connected to the C1s vacancy, which shows essentially one distinct band.

The development of a new variant of the magnetic bottle coincidence technique tailored for valence triple photoionization studies of rare gas atoms at synchrotron radiation sources is presented, overcoming the problem of high repetition rate in single-bunch operation of the storage ring. The studies of the rare gas atoms confirm that a correction of the lowest triple-ionization energy of Kr, currently listed in standard tables, is needed.

Also, single-site N1s and O1s double core ionization of the NO and N2O molecules and single-site O1s, C1s and S2p double core ionization of the OCS molecule has been studied with the magnetic bottle technique. Double core holes are of particular interest due to putatively larger chemical shifts compared to single core holes. The observed ratio between the double and single ionization energies are in all cases close or equal to 2.20.

Place, publisher, year, edition, pages
Uppsala: Acta Universitatis Upsaliensis, 2014. p. 55
Series
Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology, ISSN 1651-6214 ; 1132
National Category
Atom and Molecular Physics and Optics
Research subject
Physics with spec. in Atomic, Molecular and Condensed Matter Physics
Identifiers
urn:nbn:se:uu:diva-221128 (URN)978-91-554-8910-6 (ISBN)
Public defence
2014-05-16, sal 80121, Ångströmlaboratoriet, Lägerhyddsvägen 1, Uppsala, 13:15 (Swedish)
Opponent
Supervisors
Available from: 2014-04-24 Created: 2014-03-25 Last updated: 2014-04-29Bibliographically approved

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Andersson, EgilHedin, LageKarlsson, LeifRubensson, Jan-ErikFeifel, Raimund

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