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PHOTO-STABILITY OF SUPER-HYDROGENATED PAHs DETERMINED BY ACTION SPECTROSCOPY EXPERIMENTS
Stockholm University, Faculty of Science, Department of Physics.
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Number of Authors: 82016 (English)In: Astrophysical Journal, ISSN 0004-637X, E-ISSN 1538-4357, Vol. 832, no 1, article id 24Article in journal (Refereed) Published
Abstract [en]

We have investigated the photo-stability of pristine and super-hydrogenated pyrene cations (C16H10+m+, m = 0, 6, or 16) by means of gas-phase action spectroscopy. Optical absorption spectra and photoinduced dissociation mass spectra are presented. By measuring the yield of mass-selected photo-fragment ions as a function of laser pulse intensity, the number of photons (and hence the energy) needed for fragmentation of the carbon backbone was determined. Backbone fragmentation of pristine pyrene ions (C16H10+) requires absorption of three photons of energy just below 3 eV, whereas super-hydrogenated hexahydropyrene (C16H16+) must absorb two such photons and fully hydrogenated hexadecahydropyrene (C16H26+) only a single photon. These results are consistent with previously reported dissociation energies for these ions. Our experiments clearly demonstrate that the increased heat capacity from the additional hydrogen atoms does not compensate for the weakening of the carbon backbone when pyrene is hydrogenated. In photodissociation regions, super-hydrogenated Polycyclic Aromatic Hydrocarbons (PAHs) have been proposed to serve as catalysts for H-2 formation. Our results indicate that carbon backbone fragmentation may be a serious competitor to H-2 formation at least for small hydrogenated PAHs like pyrene.

Place, publisher, year, edition, pages
2016. Vol. 832, no 1, article id 24
Keywords [en]
ISM: molecules, photon-dominated region (PDR)
National Category
Physical Sciences
Research subject
Physics
Identifiers
URN: urn:nbn:se:su:diva-137722DOI: 10.3847/0004-637X/832/1/24ISI: 000388603600006Scopus ID: 2-s2.0-84996562114OAI: oai:DiVA.org:su-137722DiVA, id: diva2:1066140
Available from: 2017-01-17 Created: 2017-01-10 Last updated: 2022-10-18Bibliographically approved
In thesis
1. Energetic processing of complex molecules in the gas phase
Open this publication in new window or tab >>Energetic processing of complex molecules in the gas phase
2018 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Collisions between molecules and gas phase targets often lead to various intriguing processes. Such collisions may induce fragmentation of molecules that can be divided into different subsets depending on the projectile, target, and collision energy. One major part of the present research is the exploration of astrophysical relevant collision mechanisms. In collisions between polycyclic aromatic hydrocarbon (PAH) molecules or fullerenes with, for example, helium, nuclear stopping can lead to the prompt knockout of a carbon atom from the molecule. Such a vacancy in the molecular carbon backbone can be highly reactive, and lead to the formation of larger molecules. The energy dependencies of such processes are important for the understanding of astrochemical molecular growth processes, which in turn may lead to the formation of larger and more complex molecules in space. In addition, hydrogenation of PAHs changes their structures and internal properties, including their resistance against fragmentation. To better understand the effects of hydrogenation on the fragmentation of PAHs, low energy photofragmentation experiments are presented along with the collision experiments, and a detailed comparison is made between the effects of these different types of energy transfer processes.

Besides astrophysically relevant research, studies on the response of biomolecules to collisions with gas phase targets are presented. Here, the energy dependence for formation of the protonated n-butyl β-ionone Schiff base through electrocyclization of the protonated n-butylamine Schiff base of all-trans-retinal in collisions is presented. The latter is a model compound for all-trans-retinal, the chromophore of the light sensitive opsin proteins, and such studies are essential for the understanding of the operation of mammal vision.

While our collision studies are very successful, they are sometimes also limited by the experimental timescale. Therefore, we have constructed an experimental setup for ion storage and fragmentation analysis. The goal of this new experiment is to store internally hot fragments to investigate their behavior on extended timescales and as functions of internal excitation energies.

Place, publisher, year, edition, pages
Department of Physics, Stockholm University, 2018
National Category
Physical Sciences
Research subject
Physics
Identifiers
urn:nbn:se:su:diva-149602 (URN)978-91-7797-083-5 (ISBN)978-91-7797-084-2 (ISBN)
Public defence
2018-01-31, FB52, AlbaNova Universitetscentrum, Roslagstullsbacken 21, Stockholm, 13:00 (English)
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Note

At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 5: Submitted. Paper 6: Submitted.

Available from: 2018-01-08 Created: 2017-12-06 Last updated: 2022-02-28Bibliographically approved

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Publisher's full textScopusarXiv:1609.04264

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Wolf, MichaelZettergren, HenningSchmidt, Henning T.Cederquist, Henrik

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