| 1. |
- Hansen, Klavs, 1958, et al.
(författare)
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Non-scrambling of hydrogen in NH 4 + (H 2 O) 3 clusters
- 2019
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Ingår i: RSC Advances. - : Royal Society of Chemistry (RSC). - 2046-2069. ; 9:12, s. 6620-6626
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Tidskriftsartikel (refereegranskat)abstract
- We have measured the metastable decay of protonated, ammonia-doped, deuterated water clusters produced in an electrospray source, dn-NH4+(H2O)3, n = 0-6. The mass spectra show a very strong odd-even effect, consistent with a low degree of scrambling of the hydrogen bound to water and to the ammonia. The relative evaporation rate constant for light water was almost twice the one for heavy water, with the rate for mixed protium-deuterium water molecule intermediate between these two values.
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| 2. |
- Støchkel, K., et al.
(författare)
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On the influence of water on the electronic structure of firefly oxyluciferin anions from absorption spectroscopy of bare and monohydrated ions in vacuo
- 2013
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Ingår i: Journal of the American Chemical Society. - : American Chemical Society (ACS). - 0002-7863 .- 1520-5126. ; 135:17, s. 6485-6493
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Tidskriftsartikel (refereegranskat)abstract
- A complete understanding of the physics underlying the varied colors of firefly bioluminescence remains elusive because it is difficult to disentangle different enzyme-lumophore interactions. Experiments on isolated ions are useful to establish a proper reference when there are no microenvironmental perturbations. Here, we use action spectroscopy to compare the absorption by the firefly oxyluciferin lumophore isolated in vacuo and complexed with a single water molecule. While the process relevant to bioluminescence within the luciferase cavity is light emission, the absorption data presented here provide a unique insight into how the electronic states of oxyluciferin are altered by microenvironmental perturbations. For the bare ion we observe broad absorption with a maximum at 548 ± 10 nm, and addition of a water molecule is found to blue-shift the absorption by approximately 50 nm (0.23 eV). Test calculations at various levels of theory uniformly predict a blue-shift in absorption caused by a single water molecule, but are only qualitatively in agreement with experiment highlighting limitations in what can be expected from methods commonly used in studies on oxyluciferin. Combined molecular dynamics simulations and time-dependent density functional theory calculations closely reproduce the broad experimental peaks and also indicate that the preferred binding site for the water molecule is the phenolate oxygen of the anion. Predicting the effects of microenvironmental interactions on the electronic structure of the oxyluciferin anion with high accuracy is a nontrivial task for theory, and our experimental results therefore serve as important benchmarks for future calculations.
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| 3. |
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| 4. |
- Gatchell, Michael, et al.
(författare)
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Non-statistical fragmentation of PAHs and fullerenes in collisions with atoms
- 2014
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Ingår i: International Journal of Mass Spectrometry. - : Elsevier BV. - 1387-3806 .- 1873-2798. ; 365, s. 260-265
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Tidskriftsartikel (refereegranskat)abstract
- Non-statistical fragmentation processes may be important when Polycyclic Aromatic Hydrocarbon molecules (PAHs), fullerenes, or other large complex molecules collide with atoms and atomic ions. For collisions with hydrogen or helium this occurs for center-of-mass energies between a few tens to a few hundreds of electron volts and typically results in losses of single atoms. In such processes one forms much more reactive fragments than in statistical fragmentation, which instead are dominated by losses of C2- or C2H2-molecules (H-atoms) from fullerenes and PAHs, respectively. An enhanced reactivity has recently been demonstrated for van der Waals clusters of C60 molecules where prompt knockouts of single C-atoms from one of the fullerenes yield highly reactive C59+ fragments, which easily form covalent bonds with a C60 molecule inside the clusters
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| 5. |
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| 6. |
- Johansson, Henrik A. B., et al.
(författare)
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Unimolecular dissociation of anthracene and acridine cations : The importance of isomerization barriers for the C2H2 loss and HCN loss channels
- 2011
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Ingår i: Journal of Chemical Physics. - : AIP Publishing. - 0021-9606 .- 1089-7690. ; 135, s. 084304-
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Tidskriftsartikel (refereegranskat)abstract
- The loss of C2H2 is a low activation energy dissociation channel for anthracene (C14H10) and acridine (C13H9N) cations. For the latter ion another prominent fragmentation pathway is the loss of HCN. We have studied these two dissociation channels by collision induced dissociation experiments of 50 keV anthracene cations and protonated acridine, both produced by electrospray ionization, in collisions with a neutral xenon target. In addition, we have carried out density functional theory calculations on possible reaction pathways for the loss of C2H2 and HCN. The mass spectra display features of multi-step processes, and for protonated acridine the dominant first step process is the loss of a hydrogen from the N site, which then leads to C2H2/HCN loss from the acridine cation. With our calculations we have identified three pathways for the loss of C2H2 from the anthracene cation, with three different cationic products: 2-ethynylnaphthalene, biphenylene, and acenaphthylene. The third product is the one with the overall lowest dissociation energy barrier. For the acridine cation our calculated pathway for the loss of C2H2 leads to the 3-ethynylquinoline cation, and the loss of HCN leads to the biphenylene cation. Isomerization plays an important role in the formation of the non-ethynyl containing products. All calculated fragmentation pathways should be accessible in the present experiment due to substantial energy deposition in the collisions.
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| 7. |
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| 8. |
- Stockett, Mark H., et al.
(författare)
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Nonstatistical fragmentation of large molecules
- 2014
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Ingår i: Physical Review A. Atomic, Molecular, and Optical Physics. - 1050-2947 .- 1094-1622. ; 89:3
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Tidskriftsartikel (refereegranskat)abstract
- We present experimental evidence for the dominance of prompt single-atom knockout in fragmenting collisions between large polycyclic aromatic hydrocarbon cations and He atoms at center-of-mass energies close to 100 eV. Such nonstatistical processes are shown to give highly reactive fragments. We argue that nonstatistical fragmentation is dominant for any sufficiently large molecular system under similar conditions.
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| 9. |
- Sundén, Erika, 1970, et al.
(författare)
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Heat capacities of freely evaporating charged water clusters
- 2009
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Ingår i: Journal of Chemical Physics. - : AIP Publishing. - 0021-9606 .- 1089-7690. ; 130:22
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Tidskriftsartikel (refereegranskat)abstract
- We report on evaporation studies on positively charged water clusters (H$^+$(H$_2$O)$_N$) and negatively charged mixed clusters (X$^-$(H$_2$O)$_N$) with a small core ion $X$ ($X$=O$_2$,CO$_3$ or NO$_3$), in the size range $N=5$ to $300$. The clusters were produced by corona discharge in ambient air, accelerated to 50 keV and mass selected by an electromagnet. The loss of monomers during the subsequent 3.4 m free flight was recorded. The average losses are proportional to the clusters' heat capacities and this allowed the determination of size-dependent heat capacities. The values are found to increase almost linearly with clusters size for both species, with a rate of 6-8 $k_B$ per added molecule. For clusters with $N<21$ the heat capacities per molecule are lower but the incremental increase higher. For $N>21$ the values are intermediate between the bulk liquid and the solid water 0 $^o$C values.
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| 10. |
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| 11. |
- Zettergren, Henning, et al.
(författare)
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Fragmentation and ionization of C70 and C60 by slow ions of intermediate charge
- 2006
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Ingår i: European Physical Journal D. - : Springer. - 1434-6060 .- 1434-6079. ; 38:2, s. 299-306
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Tidskriftsartikel (refereegranskat)abstract
- We have measured total and coincident (with outgoing charge-state analyzed projectiles) ionization and fragmentation spectra of C 60 and C70 following collisions with Xe4+ and Kr4+ at v = 0. 06 a.u. Intact positive fullerene ions in charge states up to five (C 5+ 60 and C 5+ 70 ) are produced with both projectiles and for Kr 4++C70 collisions we even observe a small C 6+ 70 peak. The C 3+ 60 /70−2m (m = 1–7) intensity distributions are predominantly associated with the stabilization of three electrons on the projectile ( s = 3) and are significantly different for Xe 4+- and Kr4+ -projectiles. On the other hand, we find remarkable similarities in the C + 3 -C + 11 multi-fragmentation pattern regardless of projectile species (mass) although they are associated with closer encounters in which the projectile is fully neutralized ( s = 4). Simple Monte Carlo calculations of nuclear and electronic loss processes show that both these contributions are very similar in glancing Xe 4++C60 and Kr4++C60 collisions, suggesting that frontal (and more violent) collisions are strongly suppressed under the present experimental conditions. Nevertheless it is surprising that the more distant collisions ( s = 3) are projectile mass dependent, while the closer collisions (s = 4) are not. This indicates that this simple approach (although it reproduces more advanced quantum mechanical calculations for slow collisions with singly charged atomic ions rather well) is not valid for a comprehensive description of the energy transfer processes in the present collision systems involving projectiles of higher charge states.
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