| 1. |
- Ideböhn, Veronica, 1992, et al.
(författare)
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Single photon double and triple ionization of allene
- 2022
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Ingår i: Physical Chemistry Chemical Physics. - : Royal Society of Chemistry (RSC). - 1463-9076 .- 1463-9084. ; 24:2, s. 786-796
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Tidskriftsartikel (refereegranskat)abstract
- Double and triple ionization of allene are investigated using electron-electron, ion-ion, electron-electron-ion and electron-electron-ion-ion (ee, ii, eei, eeii) coincidence spectroscopies at selected photon energies. The results provide supporting evidence for a previously proposed roaming mechanism in H-3(+) formation by double ionization. The lowest vertical double ionization energy is found to be 27.9 eV, while adiabatic double ionization is not accessed by vertical ionization at the neutral geometry. The triple ionization energy is found to be close to 50 eV in agreement with theoretical predictions. The doubly charged parent ion is stable up to about 2 eV above the threshold, after which dissociations by charge separation and by double charge retention occur with comparable intensities. Fragmentation to H+ + C3H3+ starts immediately above the threshold as a slow (metastable) decay with 130.5 +/- 9.9 ns mean lifetime.
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| 2. |
- Jarraya, M., et al.
(författare)
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Doubly ionized OCS bond rearrangement upon fragmentation - experiment and theory
- 2023
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Ingår i: Physical Chemistry Chemical Physics. - 1463-9076. ; 25:29, s. 19435-19445
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Tidskriftsartikel (refereegranskat)abstract
- The dissociation of OCS2+ ions formed by photoionization of the neutral molecule at 40.81 eV is examined using threefold and fourfold electron-ion coincidence spectroscopy combined with high level quantum chemical calculations on isomeric structures and their potential energy surfaces. The dominant dissociation channel of [OCS](2+) is charge separation forming CO+ + S+ ion pairs, found here to be formed with low intensity at a lower-energy onset and with a correspondingly smaller kinetic energy release than in the more intense higher energy channel previously reported. We explain the formation of CO+ + S+ ion pairs at low as well as higher ionization energies by the existence of two predissociation channels, one involving a newly identified COS2+ metastable state. We conclude that the dominant CO+ + S+ channel with 5.2 eV kinetic energy release is reached upon OCS2+ & RARR; COS2+ isomerization, whereas the smaller kinetic energy release (of & SIM;4 eV) results from the direct fragmentation of OCS2+ (X-3 & sigma;(-)) ions. Dissociation of the COS2+ isomer also explains the existence of the minor C+ + SO+ ion pair channel. We suggest that isomerization prior to dissociation may be a widespread mechanism in dications and more generally in multiply charged ion dissociations.
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| 3. |
- Olsson, Emelie, 1993, et al.
(författare)
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An experimental and theoretical characterization of the electronic structure of doubly ionised disulfur
- 2022
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Ingår i: Scientific Reports. - : Springer Science and Business Media LLC. - 2045-2322. ; 12:1
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Tidskriftsartikel (refereegranskat)abstract
- Using time-of-flight multiple electron and ion coincidence techniques in combination with a helium gas discharge lamp and synchrotron radiation, the double ionisation spectrum of disulfur (S-2) and the subsequent fragmentation dynamics of its dication are investigated. The S-2 sample was produced by heating mercury sulfide (HgS), whose vapour at a suitably chosen temperature consists primarily of two constituents: S-2 and atomic Hg. A multi-particle-coincidence technique is thus particularly useful for retrieving spectra of S-2 from ionisation of the mixed vapour. The results obtained are compared with detailed calculations of the electronic structure and potential energy curves of S-2(2+) which are also presented. These computations are carried out using configuration interaction methodology. The experimental results are interpreted with and strongly supported by the computational results.
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| 4. |
- Eland, John H. D., 1941, et al.
(författare)
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Double and Triple Ionisation of Isocyanic Acid
- 2020
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Ingår i: Scientific Reports. - : Springer Science and Business Media LLC. - 2045-2322. ; 10
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Tidskriftsartikel (refereegranskat)abstract
- Double and triple ionisation spectra of the reactive molecule isocyanic acid (HNCO) have been measured using multi-electron and ion coincidence techniques combined with synchrotron radiation and compared with high-level theoretical calculations. Vertical double ionisation at an energy of 32.8±0.3eV forms the 3A” ground state in which the HNCO2+ ion is long lived. The vertical triple ionisation energy is determined as 65±1eV. The core-valence double ionisation spectra resemble the valence photoelectron spectrum in form, and their main features can be understood on the basis of a simple and rather widely applicable Coulomb model based on the characteristics of the molecular orbitals from which electrons are removed. Characteristics of the most important dissociation channels are examined and discussed.
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| 5. |
- Ideböhn, Veronica, 1992, et al.
(författare)
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Symmetry breaking in core-valence double ionisation of allene
- 2023
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Ingår i: Communications Chemistry. - : Springer Nature. - 2399-3669. ; 6:1
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Tidskriftsartikel (refereegranskat)abstract
- Allene serves as a model to study multiple ionization of organic molecules. Here, the authors use synchrotron radiation-based multi-particle coincidence techniques and high-level ab initio calculations to propose a simple physical model to elucidate the symmetry breaking in core-valence double ionization of allene. Conventional electron spectroscopy is an established one-electron-at-the-time method for revealing the electronic structure and dynamics of either valence or inner shell ionized systems. By combining an electron-electron coincidence technique with the use of soft X-radiation we have measured a double ionisation spectrum of the allene molecule in which one electron is removed from a C1s core orbital and one from a valence orbital, well beyond Siegbahns Electron-Spectroscopy-for-Chemical-Analysis method. This core-valence double ionisation spectrum shows the effect of symmetry breaking in an extraordinary way, when the core electron is ejected from one of the two outer carbon atoms. To explain the spectrum we present a new theoretical approach combining the benefits of a full self-consistent field approach with those of perturbation methods and multi-configurational techniques, thus establishing a powerful tool to reveal molecular orbital symmetry breaking on such an organic molecule, going beyond Lowdins standard definition of electron correlation.
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| 6. |
- Jarraya, M., et al.
(författare)
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State selective fragmentation of doubly ionized sulphur dioxide
- 2021
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Ingår i: Scientific Reports. - : Springer Science and Business Media LLC. - 2045-2322. ; 11:1
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Tidskriftsartikel (refereegranskat)abstract
- Using multi-electron-ion coincidence measurements combined with high level calculations, we show that double ionisation of SO2 at 40.81 eV can be state selective. It leads to high energy products, in good yield, via a newly identified mechanism, which is likely to apply widely to multiple ionisation by almost all impact processes.
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| 7. |
- Koulentianos, Dimitris, 1987, et al.
(författare)
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Formation and relaxation of K-2 and K-2V double-core-hole states in n-butane
- 2022
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Ingår i: Journal of Chemical Physics. - : AIP Publishing. - 0021-9606 .- 1089-7690. ; 157:4
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Tidskriftsartikel (refereegranskat)abstract
- Using a magnetic bottle multi-electron time-of-flight spectrometer in combination with synchrotron radiation, double-core-hole pre-edge and continuum states involving the K-shell of the carbon atoms in n-butane ( n-C4H10) have been identified, where the ejected core electron(s) and the emitted Auger electrons from the decay of such states have been detected in coincidence. An assignment of the main observed spectral features is based on the results of multi-configurational self-consistent field (MCSCF) calculations for the excitation energies and static exchange (STEX) calculations for energies and intensities. MCSCF results have been analyzed in terms of static and dynamic electron relaxation as well as electron correlation contributions to double-core-hole state ionization potentials. The analysis of applicability of the STEX method, which implements the one-particle picture toward the complete basis set limit, is motivated by the fact that it scales well toward large species. We find that combining the MCSCF and STEX techniques is a viable approach to analyze double-core-hole spectra.
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| 8. |
- Wallner, Måns, 1992, et al.
(författare)
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Abiotic molecular oxygen production—Ionic pathway from sulfur dioxide
- 2022
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Ingår i: Science Advances. - : American Association for the Advancement of Science (AAAS). - 2375-2548. ; 8:33
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Tidskriftsartikel (refereegranskat)abstract
- Molecular oxygen, O2, is vital to life on Earth and possibly also on exoplanets. Although the biogenic processes leading to its accumulation in Earth’s atmosphere are well understood, its abiotic origin is still not fully established. Here, we report combined experimental and theoretical evidence for electronic state–selective production of O2 from SO2, a chemical constituent of many planetary atmospheres and one that played an important part on Earth in the Great Oxidation Event. The O2 production involves dissociative double ionization of SO2 leading to efficient formation of the O+2 O 2 + ion, which can be converted to abiotic O2 by electron neutralization or by charge exchange. This formation process may contribute substantially to the abundance of O2 and related ions in planetary atmospheres, such as the Jovian moons Io, Europa, and Ganymede. We suggest that this sort of ionic pathway for the formation of abiotic O2 involving multiply charged molecular ion decomposition may also exist for other atmospheric and planetary molecules.
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| 9. |
- Wallner, Måns, 1992, et al.
(författare)
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Coulomb Explosion of CD3I induced by single photon deep inner shell ionisation
- 2020
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Ingår i: Scientific Reports. - : Springer Science and Business Media LLC. - 2045-2322. ; 10
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Tidskriftsartikel (refereegranskat)abstract
- L-shell ionisation and subsequent coulomb explosion of fully deuterated methyl iodide, cD3i, irradiated with hard X-rays has been examined by a time-of-flight multi-ion coincidence technique. The core vacancies relax efficiently by Auger cascades, leading to charge states up to 16+. the dynamics of the Coulomb explosion process are investigated by calculating the ions’ flight times numerically based on a geometric model of the experimental apparatus, for comparison with the experimental data. A parametric model of the explosion, previously introduced for multi-photon induced coulomb explosion, is applied in numerical simulations, giving good agreement with the experimental results for medium charge states. Deviations for higher charges suggest the need to include nuclear motion in a putatively more complete model. Detection efficiency corrections from the simulations are used to determine the true distributions of molecular charge states produced by initial L1, L2 and L3 ionisation.
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