| 1. |
- Kivimäki, Antti, et al.
(författare)
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Yields and Time-of-Flight Spectra of Neutral High-Rydberg Fragments at the K Edges of the CO2 Molecule
- 2016
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Ingår i: The Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory. - : American Chemical Society (ACS). - 1089-5639. ; 120:25, s. 4360-4367
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Tidskriftsartikel (refereegranskat)abstract
- We have studied the production of neutral fragments in high-Rydberg (HR) states at the C 1s and O 1s edges of the CO2 molecule by performing two kinds of experiments. First, the yields of neutral HR fragments were measured indirectly by ionizing such fragments in a static electric field and by collecting resulting singly charged positive ions as a function of the photon energy. Such measurements reveal not only excitations below the core ionization thresholds but also thresholds for single core-hole and shakeup photoionization. Second, we obtained the mass spectra of neutral HR fragments at selected photon energies by exploiting pulsed field ionization; they show atomic fragments C(HR) and O(HR). We discuss dissociation pathways leading to the production of neutral HR fragments in core excitation and ionization of CO2.
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| 2. |
- Kivimäki, Antti, et al.
(författare)
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Soft X-ray Induced Production of Neutral Fragments in High-Rydberg States at the O 1s Ionization Threshold of the Water Molecule
- 2021
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Ingår i: Journal of Physical Chemistry A. - : American Chemical Society (ACS). - 1089-5639 .- 1520-5215. ; 125:3, s. 713-720
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Tidskriftsartikel (refereegranskat)abstract
- Dissociation of water molecules after soft X-ray absorption can yield neutral fragments in high-Rydberg (HR) states. We have studied the production of such fragments by field ionization and ion time-of-flight (TOF) spectrometry. Neutral HR fragments are created at all resonances below the O 1s ionization potential (IP) and particularly within 1 eV above the O 1s IP. The latter effect is due to the recapture of the O 1s photoelectrons into HR orbitals of the molecular water ion after the emission of a fast Auger electron. H2O+(HR) fragments subsequently dissociate, yielding neutral H(HR) and O(HR) fragments, as were found by measuring the TOF spectra by pulsed field ionization. Such measurements were carried out at the O 1s → 4a1 and 2b2 resonances as well as just above the O 1s IP. The TOF spectra also reveal two series of oscillatory structures that are attributed to quantum beats involving Lyman emission in one of the series and field ionization of H(HR) fragments in the other series.
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| 3. |
- Wasowicz, Tomasz J., et al.
(författare)
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Two-body dissociation of isoxazole following double photoionization - an experimental PEPIPICO and theoretical DFT and MP2 study
- 2023
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Ingår i: Physical Chemistry Chemical Physics. - 1463-9076. ; 25:46, s. 31655-31666
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Tidskriftsartikel (refereegranskat)abstract
- The dissociative double photoionization of isoxazole molecules has been investigated experimentally and theoretically. The experiment has been carried out in the 27.5-36 eV photon energy range using vacuum ultraviolet (VUV) synchrotron radiation excitation combined with ion time-of-flight (TOF) spectrometry and photoelectron-photoion-photoion coincidence (PEPIPICO) technique. Five well-resolved two-body dissociation channels have been identified in the isoxazole's coincidence maps, and their appearance energies have been determined. The coincidence yield curves of these dissociation channels have been obtained in the photon energy ranges from their appearance energies up to 36 eV. The double photoionization of isoxazole produces a C3H3NO2+ transient dication, which decomposes into fragments differing from previously reported photofragmentation products of isoxazole. We have found no evidence of pathways leading to the C3H2NO+, HCN+, C2H2O+, C3HN+, or C2H2+ fragments or their neutral counterparts that have been observed in previous neutral photodissociation and single photoionization studies. Instead, the dissociation of isoxazole after the ejection of two electrons is bond-selective and is governed by two reactions, HCO+ + H2CCN+ and H2CO+ + HCCN+, whose appearance energies are 28.6 (±0.3) and 29.4 (±0.3) eV, respectively. A third dissociation channel turns out to be a variant of the most intense channel (HCO+ + H2CCN+), where one of the fragment ions contains a heavy isotope. Two minor dissociation channels occurring at higher energies, CO+ + CH3CN+ and CN+ + H3CCO+, are also identified. The density functional and ab initio quantum chemical calculations have been performed to elucidate the dissociative charge-separating mechanisms and determine the energies of the observed photoproducts. The present work unravels hitherto unexplored photodissociation mechanisms of isoxazole and thus provides deeper insight into the photophysics of five-membered heterocyclic molecules containing two heteroatoms.
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| 4. |
- Wasowicz, Tomasz J., et al.
(författare)
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Vacuum ultraviolet photoionization and ionic fragmentation of the isoxazole molecules
- 2020
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Ingår i: International Journal of Mass Spectrometry. - : Elsevier BV. - 1387-3806. ; 449
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Tidskriftsartikel (refereegranskat)abstract
- The photofragmentation of the isoxazole molecules producing ionized atomic and molecular fragments was investigated in the photon energy range of 9–32 eV, using synchrotron radiation excitation combined with ion time-of-flight spectrometry. Twenty-one well resolved cations were identified in the mass spectra of the isoxazole, and their appearance energies were determined. The yield curves of these cations were obtained in the photon energy ranges from their appearance energies up to 32 eV. Moreover, the total ion yield of isoxazole was recorded with high precision in the photon energy range of 9.9–10.5 eV. This allowed the determination of the adiabatic ionization energy of 9.96 (0.02) eV in excellent agreement with earlier spectroscopic studies. Our results show that the dissociative ionization of isoxazole starts from the ring-opening and isomerization of isoxazole, and further it follows strictly through its ionic states. Possible ionic fragmentation channels yielding particular ions are discussed.
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