| 1. |
- Fischer, D., et al.
(författare)
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Importance of Thomas single-electron transfer in fast p-He collisions
- 2010
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Ingår i: Physical Review A. Atomic, Molecular, and Optical Physics. - 1050-2947 .- 1094-1622. ; 81:1, s. 12714-
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Tidskriftsartikel (refereegranskat)abstract
- We report experimental angular differential cross sections for nonradiative single-electron capture in p-He collisions (p + He -> H + He+) with a separate peak at the 0.47 mrad Thomas scattering angle for energies in the 1.3-12.5 MeV range. We find that the intensity of this peak scales with the projectile velocity as v(P)(-11). This constitutes the first experimental test of the prediction from 1927 by L. H. Thomas [Proc. R. Soc. 114, 561 (1927)]. At our highest energy, the peak at the Thomas angle contributes with 13.5% to the total integrated nonradiative single-electron capture cross section.
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| 2. |
- Haag, Nicole, et al.
(författare)
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Collisions with biomolecules embedded in smallwater clusters
- 2009
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Konferensbidrag (refereegranskat)abstract
- We have studied fragmentation of water embedded adenosine 5’-monophosphate(AMP) anions after collisions with neutral sodium atoms. At a collision energy of 50 keV,loss of water molecules from the collisionally excited cluster ions is the dominant process andfragmentation of the AMP itself is almost completely prohibited if the number of attachedwater molecules is larger than 13. However, regardless of the initial number of water moleculesattached to the ion, capture of an electron, i.e. formation of a dianion, always leads to loss ofa single hydrogen atom accompanied by evaporation of water molecules. This damaging effectbecomes more important as the size of the water cluster increases, which is just the oppositeto the protective behavior observed for collision induced dissociation (CID) without electrontransfer. For both cases, the loss of water molecules within the experimental time frame isqualitatively well described by means of a common model of an evaporative ensemble. Thesesimulations, however, indicate that characteristically different distributions of internal energyare involved in CID and electron capture induced dissociation.
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| 3. |
- Haag, Nicole, et al.
(författare)
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Electron capture induced dissociation of doubly protonated pentapeptides : Dependence on molecular structure and charge separation
- 2011
-
Ingår i: Journal of Chemical Physics. - : AIP Publishing. - 0021-9606 .- 1089-7690. ; 134:3, s. 035102-
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Tidskriftsartikel (refereegranskat)abstract
- We have studied electron capture induced dissociation of a set of doubly protonated pentapeptides, all composed of one lysine (K) and either four glycine (G) or four alanine (A) residues, as a function of the sequence of these building blocks. Thereby the separation of the two charges, sequestered on the N-terminal amino group and the lysine side chain, is varied. The characteristic cleavage of N–Cα bonds is observed for all peptides over the whole backbone length, with the charge carrying fragments always containing K. The resulting fragmentation patterns are very similar if G is replaced by A. In the case of [XKXXX+2H]2+ (X=A or G), a distinct feature is observed in the distribution of backbone cleavage fragments and the probability for ammonia loss is drastically reduced. This may be due to an isomer with an amide oxygen as protonation site giving rise to the observed increase in breakage at a specific site in the molecule. For the other peptides, a correlation with the distance between amide oxygen and the charge at the lysine side chain has been found. This may be an indication that it is only the contribution from this site to the charge stabilization of the amide π* orbitals which determines relative fragment intensities. For comparison, complexes with two crown ether molecules have been studied as well. The crown ether provides a shielding of the charge and prevents the peptide from folding and internal hydrogen bonding, which leads to a more uniform fragmentation behavior.
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| 4. |
- Hartman, Henrik, et al.
(författare)
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First storage of ion beams in the Double Electrostatic Ion-Ring Experiment : DESIREE
- 2013
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Ingår i: Review of Scientific Instruments. - : American Institute of Physics (AIP). - 0034-6748 .- 1089-7623. ; 84:5
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Tidskriftsartikel (refereegranskat)abstract
- We report on the first storage of ion beams in the Double ElectroStatic Ion Ring ExpEriment, DESIREE, at Stockholm University. We have produced beams of atomic carbon anions and small carbon anion molecules (Cn-, n = 1, 2, 3, 4) in a sputter ion source. The ion beams were accelerated to 10 keV kinetic energy and stored in an electrostatic ion storage ring enclosed in a vacuum chamber at 13 K. For 10 keV C2- molecular anions we measure the residual-gas limited beam storage lifetime to be 448 s +/- 18 s with two independent detector systems. Using the measured storage lifetimes we estimate that the residual gas pressure is in the 10-14 mbar range. When high current ion beams are injected, the number of stored particles does not follow a single exponential decay law as would be expected for stored particles lost solely due to electron detachment in collision with the residual-gas. Instead, we observe a faster initial decay rate, which we ascribe to the effect of the space charge of the ion beam on the storage capacity.
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| 5. |
- Holm, Anne I. S., et al.
(författare)
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Dissociation and multiple ionization energies for five polycyclic aromatic hydrocarbon molecules
- 2011
-
Ingår i: Journal of Chemical Physics. - : AIP Publishing. - 0021-9606 .- 1089-7690. ; 134:4, s. 044301-
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Tidskriftsartikel (refereegranskat)abstract
- We have performed density functional theory calculations for a range of neutral, singly, and multiply charged polycyclic aromatic hydrocarbons (PAHs), and their fragmentation products for H-, H+-, C2H2-, and C2H2+-emissions. The adiabatic and vertical ionization energies follow linear dependencies as functions of charge state for all five intact PAHs (naphthalene, biphenylene, anthracene, pyrene, and coronene). First estimates of the total ionization and fragmentation cross sections in ion-PAH collisions display markedly different size dependencies for pericondensed and catacondensed PAH species, reflecting differences in their first ionization energies. The dissociation energies show that the PAHq+-molecules are thermodynamically stable for q <= 2 (naphthalene, biphenylene, and anthracene), q <= 3 (pyrene), and q <= 4 (coronene). PAHs in charge states above these limits may also survive experimental time scales due to the presence of reaction barriers as deduced from explorations of the potential energy surface regions for H+-emissions from all five PAHs and for C2H2+-emission from naphthalene - the smallest PAH.
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| 6. |
- Holm, Anne I. S., et al.
(författare)
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Ions Colliding with Cold Polycyclic Aromatic Hydrocarbon Clusters
- 2010
-
Ingår i: Physical Review Letters. - 0031-9007 .- 1079-7114. ; 105:21, s. 213401-
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Tidskriftsartikel (refereegranskat)abstract
- We report the first experimental study of ions interacting with clusters of polycyclic aromatic hydrocarbon (PAH) molecules. Collisions between 11.25 keV He-3(+) or 360 keV Xe-129(20+) and weakly bound clusters of one of the smallest PAH molecules, anthracene, show that C14H10 clusters have much higher tendencies to fragment in ion collisions than other weakly bound clusters. The ionization is dominated by peripheral collisions in which the clusters, very surprisingly, are more strongly heated by Xe20+ collisions than by He+ collisions. The appearance size is k = 15 for [C14H10](k)(2+).
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| 7. |
- Johansson, Henrik A. B., 1979-
(författare)
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Ionization and Fragmentation of Complex Molecules and Clusters : Biomolecules and Polycyclic Aromatic Hydrocarbons
- 2011
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- This work deals with ionization and fragmentation of biomolecules and polycyclic aromatic hydrocarbon (PAH) molecules. They are studied in the gas phase both as isolated molecules and as weakly bound clusters. The purpose of the experimental and theoretical investigations are to elucidate charge and energy transfer and related redistribution processes, as well as fragmentation behaviors. The first part of this thesis presents results from studies on biomolecular ions, in particular nucleotides and peptides, which are primarily examined in electron capture induced dissociation processes. These investigations are relevant for the better understanding of radiation damage to DNA and processes involved in the sequencing of proteins. It is found that the immediate environment have a decisive influence on the fragmentation behaviors. Evaporation of surrounding molecules protect the biomolecules, but their effect on the electronic structure may also enhance or suppress different fragmentation channels. In the second part of the thesis, results from studies on PAH molecules are presented. Experimentally, their properties are mainly probed through collisions with atomic ion projectiles having kilo-electronvolt kinetic energies. As a widespread pollutant on Earth, and as a family of abundant molecules in space, PAHs are not only relevant from an environmental and health perspective, but they are also important for the understanding of the universe. The present results relate to the stabilities of these molecules, both in isolated form and in clusters, when heated or multiply ionized. It is found to be easier to remove several electrons from clusters of PAH molecules than from isolated PAHs, and fission processes determine their ultimate stabilities. Heated low-charge state clusters of PAHs undergo long evaporation sequences once these have started. For isolated and heated PAHs, internal structural rearrangements are demonstrated to be important in the fragmentation processes.
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| 8. |
- Johansson, Henrik A. B., et al.
(författare)
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Ionization and fragmentation of polycyclic aromatic hydrocarbon clusters in collisions with keV ions
- 2011
-
Ingår i: Physical Review A. Atomic, Molecular, and Optical Physics. - 1050-2947 .- 1094-1622. ; 84:4, s. 043201-
-
Tidskriftsartikel (refereegranskat)abstract
- We report on an experimental study of the ionization and fragmentation of clusters of k polycyclic aromatic hydrocarbon (PAH) molecules using anthracene, C14H10, or coronene, C24H12. These PAH clusters are moderately charged and strongly heated in small impact parameter collisions with 22.5-keV He2+ ions, after which they mostly decay in long monomer evaporation sequences with singly charged and comparatively cold monomers as dominating end products. We describe a simple cluster evaporation model and estimate the number of PAH molecules in the clusters that have to be hit by He2+ projectiles for such complete cluster evaporations to occur. Highly charged and initially cold clusters are efficiently formed in collisions with 360-keV Xe20+ ions, leading to cluster Coulomb explosions and several hot charged fragments, which again predominantly yield singly charged, but much hotter, monomer ions than the He2+ collisions. We present a simple formula, based on density-functional-theory calculations, for the ionization energy sequences as functions of coronene cluster size, rationalized in terms of the classic electrostatic expression for the ionization of a charged conducting object. Our analysis indicates that multiple electron removal by highly charged ions from a cluster of PAH molecules rapidly may become more important than single ionization as the cluster size k increases and that this is the main reason for the unexpectedly strong heating in these types of collisions.
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| 9. |
- Johansson, Henrik A. B., et al.
(författare)
-
Unimolecular dissociation of anthracene and acridine cations : The importance of isomerization barriers for the C2H2 loss and HCN loss channels
- 2011
-
Ingår i: Journal of Chemical Physics. - : AIP Publishing. - 0021-9606 .- 1089-7690. ; 135, s. 084304-
-
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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| 10. |
- Johansson, Henrik, 1979-
(författare)
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Fragmentation of Amino Acids and Microsolvated Peptides and Nucleotides using Electrospray Ionization Tandem Mass Spectrometry
- 2010
-
Licentiatavhandling (övrigt vetenskapligt/konstnärligt)abstract
- This thesis presents three different series of high energy (keV) collision experiments as well as a brief scientific introduction to the field. In the first series, protonated glycine and leucine were collided with carbon dioxide and a beam attenuation method was applied to determine their total fragmentation cross sections. A technique was also presented for how to restore the resolution in mass spectra obtained with a hemispherical electrostatic analyzer followed by a position sensitive detector (micro-channel plate equipped with a resistive anode). In the second series of experiments, Collision Induced Dissociation (CID) and Electron Capture Induced Dissociation (ECID) studies were performed on the nucleotide adenosine 5'-monophosphate anion (AMP-) in water complexes. The two dissociation techniques revealed different fragmentation patterns and a numerical solvent evaporation model was used to interpret the spectra. It was then found that the CID and ECID processes were associated with different internal energy distributions. The third experiment concerned ECID of the protonated dipeptide glycine-alanine ([GA+H]+) in complexes with water, methanol, acetonitrile or crown ether. Depending on the attached molecular species, different ratios between the two competing channels ammonia loss and N-Cα bond cleavage were observed. Quantum chemical calculations revealed that a notable shift in the location of the captured electron occurred for the case of two acetonitriles and one crown ether compared to the bare ion and the ion in complexes with either water or methanol. Finally, this thesis will discuss developments of the electrospray ionization platform as well as the new Double ElectroStatic IonRing ExpEriment (DESIREE) facility.
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| 11. |
- Lawicki, A., et al.
(författare)
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Multiple ionization and fragmentation of isolated pyrene and coronene molecules in collision with ions
- 2011
-
Ingår i: Physical Review A. Atomic, Molecular, and Optical Physics. - 1050-2947 .- 1094-1622. ; 83:2, s. 022704-
-
Tidskriftsartikel (refereegranskat)abstract
- The interaction of multiply charged ions (He2+, O3+, and Xe20+) with gas-phase pericondensed polycyclic aromatic hydrocarbon (PAH) molecules of coronene (C24H12) and pyrene (C16H10) is studied for low-velocity collisions (v <= 0.6 a.u.). The mass spectrometric analysis shows that singly and up to quadruply charged intact molecules are important reaction products. The relative experimental yields are compared with the results of a simple classical over-the-barrier model. For higher molecular charge states, the experimental yields decrease much more strongly than the model predictions due to the instabilities of the multiply charged PAH molecules. Even-odd oscillations with the number of carbon atoms, n, in the intensity distributions of the CnHx+ fragments indicate a linear chain structure of the fragments similar to those observed for ion-C60 collisions. The latter oscillations are known to be due to dissociation energy differences between even-and odd-n Cn-chain molecules. For PAH molecules, the average numbers of H atoms attached to the CnHx chains are larger for even-n reflecting acetylenic bond systems.
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| 12. |
- Liu, B., et al.
(författare)
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Electron capture induced dissociation of nucleotide anions in water nanodroplets
- 2008
-
Ingår i: Journal of Chemical Physics. - : AIP Publishing. - 0021-9606 .- 1089-7690. ; 128:7, s. 075102-
-
Tidskriftsartikel (refereegranskat)abstract
- We have studied the outcome of collisions between the hydrated nucleotide anion adenosine 5′-monophosphate (AMP) and sodium. Electron capture leads to hydrogen loss as well as water evaporation regardless of the initial number m of water molecules attached to the parent ion (m ⩽ 16). The yield of dianions with microsecond lifetimes increases strongly with m, which is explained from dielectric screening of the two charges by the water nanodroplet. For comparison, collision induced dissociation results in water losses with no or very little damage of the AMP molecule itself.
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| 13. |
- Misra, Deepankar, et al.
(författare)
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Two-Center Double-Capture Interference in Fast He2++H2 Collisions
- 2009
-
Ingår i: Physical Review Letters. - 0031-9007 .- 1079-7114. ; 102:15, s. 153201-
-
Tidskriftsartikel (refereegranskat)abstract
- We report the first observation of Young-type interference effects in a two-electron transfer process. These effects change strongly as the projectile velocity changes in fast (1.2 and 2.0 MeV) He^{2+}-H_2 collisions as manifested in strong variations of the double-electron capture rates with the H_2 orientation. This is consistent with fully quantum mechanical calculations, which ignore sequential electron transfer, and a simple projectile de Broglie wave picture assuming that two-electron transfer probabilities are higher in collisions where the projectile passes close to either one of the H_2 nuclei.
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| 14. |
- Reinhed, Peter, et al.
(författare)
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Cryogenic keV ion-beam storage in ConeTrap - a tool for ion-temperature control
- 2010
-
Ingår i: Nuclear Instruments and Methods in Physics Research Section A. - : Elsevier B.V.. - 0168-9002 .- 1872-9576. ; 621:1-3, s. 83-90
-
Tidskriftsartikel (refereegranskat)abstract
- We have tested the ion-storage capabilities of the compact triple-electrode electrostatic ion-beam trap, ConeTrap, down to cryogenic temperatures. The low-temperature operation of this electrostatic storage device is an important test for the double electrostatic ion-ring experiment, DESIREE, which is presently under construction at Stockholm University. In the present work we measured the pressure dependent storage lifetimes of 2.5 keV He+ and 2.8 keV Ar+ ion beams in ConeTrap at temperatures down to 28 K and pressures down to 1.3·10-10 mbar. The so far longest measured ion storage lifetime using this system is 21.5±3.8 s for Ar+ ions. The present combination of ConeTrap and the cryogenic experimental chamber was recently applied in the first black-body correction-free measurement of the lifetime of the metastable He- ion at 10 K [Phys. Rev. Lett. 103, 213002(2009)].
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| 15. |
- Reinhed, Peter, et al.
(författare)
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Precision lifetime measurements of He- in a cryogenic electrostatic ion-beam trap
- 2009
-
Ingår i: Physical Review Letters. - 0031-9007 .- 1079-7114. ; 103:21, s. 213002-
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Tidskriftsartikel (refereegranskat)abstract
- We have developed a small purely electrostatic ion-beam trap which may be operated in thermal equilibrium at precisely controlled temperatures down to 10 K. Thus, we avoid magnetic field induced mixing of quantum states and may effectively eliminate any influence from absorption of photons from black-body radiation. We report the first correction free measurements of the lifetimes of the 1s2s2p 4PoJ state of 4He- and the high precision result 359.0±0.7 μs for the J=5/2 level. The lifetimes for the J=3/2 and J=1/2 levels are determined to be 12.3±0.5 and 7.8±1.0 μs, respectively.
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| 16. |
- Rousseau, P., et al.
(författare)
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Low energy ions interacting with anthracene molecules and clusters
- 2012
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Ingår i: Nuclear Instruments and Methods in Physics Research Section B. - : Elsevier BV. - 0168-583X .- 1872-9584. ; 279, s. 140-143
-
Tidskriftsartikel (refereegranskat)abstract
- The interaction of slow ions (nu similar to 0.4 au.) with a small polycyclic aromatic hydrocarbon, namely anthracene (C14H10), is studied in the gas-phase either with the isolated molecule or with a pure cluster target. We discuss the ionization and fragmentation of the molecule with respect to the projectile charge state, i.e. for singly charged He+ ions and for multiply charged Xe20+. ions. For the isolated C14H10, single or multiple ionization of the molecule occurs under ion impact. The (multi) cation relative yields are compared with those obtained by other ionization methods (electron and fs-laser). The molecular dissociation occurs by loss of hydrogen and small hydrocarbon molecules, leading to the formation of CnHx cations. The interaction of Xe20+ with C14H10 clusters gives surprising results, i.e. the emission of hotter monomer compared to the interaction with He+.
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| 17. |
- Schmidt, Henning, et al.
(författare)
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DESIREE as a new tool for interstellar ion chemistry
- 2008
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Ingår i: International Journal of Astrobiology. - 1473-5504 .- 1475-3006. ; 7:3-4, s. 205-208
-
Tidskriftsartikel (refereegranskat)abstract
- A novel cryogenic electrostatic storage device consisting of two ion-beam storage rings with a common straight section for studies of interactions between oppositely charged ions at low and well-defined relative velocities is under construction at Stockholm University. Here we consider the prospect of using this new tool to measure cross-sections and rate coefficients for mutual neutralization reactions of importance in interstellar ion chemistry in general and specifically in cosmic pre-biotic ion chemistry.
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| 18. |
- Schmidt, Henning, et al.
(författare)
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Evidence of Wave-Particle Duality for Single Fast Hydrogen Atoms
- 2008
-
Ingår i: Physical Review Letters. - 0031-9007 .- 1079-7114. ; 101:8, s. 083201-
-
Tidskriftsartikel (refereegranskat)abstract
- We report the direct observation of interference effects in a Young's double-slit experiment where the interfering waves are two spatially separated components of the de Broglie wave of single 1.3 MeV hydrogen atoms formed close to either target nucleus in H+ + H2 electron-transfer collisions. Quantum interference strongly influences the results even though the hydrogen atoms have a de Broglie wavelength, \lambda_dB, as small as 25 fm.
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| 19. |
- Seitz, Fabian, 1980-, et al.
(författare)
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Polycyclic aromatic hydrocarbon-isomer fragmentation pathways : Case study for pyrene and fluoranthene molecules and clusters
- 2011
-
Ingår i: Journal of Chemical Physics. - : AIP Publishing. - 0021-9606 .- 1089-7690. ; 135:6, s. 064302-
-
Tidskriftsartikel (refereegranskat)abstract
- We report on measurements of the ionization and fragmentation of polycyclic aromatic hydrocarbon (PAH) targets in Xe(20+) + C(16)H(10) and Xe(20+) + [C(16)H(10)](k) collisions and compare results for the two C(16)H(10) isomers: pyrene and fluoranthene. For both types of targets, i.e., for single PAH molecules isolated in vacuum or for isomerically pure clusters of one of the molecules, the resulting fragment spectra are surprisingly similar. However, we do observe weak but significant isomer effects. Although these are manifested in very different ways for the monomer and cluster targets, they both have at their roots small differences (<2.5 eV) between the total binding energies of neutral, and singly and multiply charged pyrene and fluoranthene monomers. The results will be discussed in view of the density functional theory calculations of ionization and dissociation energies for fluoranthene and pyrene. A simple classical over-the-barrier model is used to estimate cross sections for single-and multiple-electron transfer between PAHs and ions. Calculated single and multiple ionization energies, and the corresponding model PAH ionization cross sections, are given.
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| 20. |
- 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
-
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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| 21. |
- Wyer, Jean Ann, et al.
(författare)
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On the hydrogen loss from protonated nucleobases after electronic excitation or collisional electron capture
- 2009
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Ingår i: European journal of mass spectrometry. - : SAGE Publications. - 1469-0667 .- 1751-6838. ; 15, s. 681-688
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Tidskriftsartikel (refereegranskat)abstract
- In this work, we have subjected protonated nucleobases MH+ (M = guanine, adenine, thymine, uracil and cytosine) to a range of experiments that involve high-energy (50 keV) collision induced dissociation and electron capture induced dissociation. In the latter case, both neutralisation reionisation and charge reversal were done. For the collision induced dissociation experiments, the ions interacted with O2. In neutral reionisation, caesium atoms were used as the target gas and the protonated nucleobases captured electrons to give neutrals. These were reionised to cations a microsecond later in collisions with O2. In choosing Cs as the target gas, we have assured that the first electron transfer process is favourable (by about 0.1–0.8 eV depending on the base). In the case of protonated adenine, charge reversal experiments (two Cs collisions) were also carried out, with the results corroborating those from the neutralisation reionisation experiments. We find that while collisional excitation of protonated nucleobases in O2 may lead to hydrogen loss with limited probabilities, this channel becomes dominant for electron capture events. Indeed, when sampling reionised neutrals on a microsecond timescale, we see that the ratio between MH+ and M+ is 0.2–0.4 when one electron is captured from Cs. There are differences in these ratios between the bases but no obvious correlation with recombination energies was found.
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| 22. |
- Zettergren, Henning, et al.
(författare)
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Electron-Capture-Induced Dissociation of Microsolvated Di- and > Tripeptide Monocations : Elucidation of Fragmentation Channels from > Measurements of Negative Ions
- 2009
-
Ingår i: ChemPhysChem. - : Wiley. - 1439-4235 .- 1439-7641. ; 10:9-10, s. 1619-1623
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Tidskriftsartikel (refereegranskat)abstract
- The branching ratio between ammonia loss and NCα bond cleavage of singly charged microsolvated peptides after electron capture from cesium depends on the solvent molecule attached. Density functional calculations reveal that for [GA+H]+(CE) (G=glycine, A=alanine, CE=crown ether), the singly occupied molecular orbital of the neutral radical is located mainly on the amide group (see picture). The results from an experimental study of bare and microsolvated peptide monocations in high-energy collisions with cesium vapor are reported. Neutral radicals form after electron capture from cesium, which decay by H loss, NH3 loss, or NCα bond cleavage into characteristic z. and c fragments. The neutral fragments are converted into negatively charged species in a second collision with cesium and are identified by means of mass spectrometry. For protonated GA (G=glycine, A=alanine), the branching ratio between NH3 loss and NCα bond cleavage is found to strongly depend on the molecule attached (H2O, CH3CN, CH3OH, and 18-crown-6 ether (CE)). Addition of H2O and CH3OH increases this ratio whereas CH3CN and CE decrease it. For protonated AAA ([AAA+H]+), a similar effect is observed with methanol, while the ratio between the z1 and z2 fragment peaks remains unchanged for the bare and microsolvated species. Density functional theory calculations reveal that in the case of [GA+H]+(CE), the singly occupied molecular orbital is located mainly on the amide group in accordance with the experimental results.
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| 23. |
- Anderson, Emma K., et al.
(författare)
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Decays of excited silver-cluster anions Agn, n=4 to 7, in the Double ElectroStatic Ion Ring ExpEriment
- 2018
-
Ingår i: Physical Review A: covering atomic, molecular, and optical physics and quantum information. - 2469-9926 .- 2469-9934. ; 98:2
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Tidskriftsartikel (refereegranskat)abstract
- Spontaneous decays of small, hot silver-cluster anions Ag-n(-), n = 4-7, have been studied using one of the rings of the Double ElectroStatic Ion Ring ExpEriment (DESIREE). Observation of these decays over very long time scales is possible due to the very low residual gas pressure (similar to 10(-14)) and cryogenic (13 K) operation of DESIREE. The yield of neutral particles from stored beams of Ag-6(-) and Ag-2(-) anions were measured for 100 milliseconds and were found to follow single power-law behavior with millisecond time-scale exponential cutoffs. The Ag-4(-) and Ag-5(-) anions were stored for 60 s and the observed decays show two-component power-law behaviors. We present calculations of the rate constants for electron detachment from and fragmentation of Ag-4(-) and Ag-5(-). In these calculations, we assume that the internal energy distribution of the clusters are flat and with this we reproduce the early steep parts of the experimentally measured decay curves for Ag-4(-) and Ag-5(-) which extends to tens and hundreds of milliseconds, respectively. The fact that the calculations reproduce the early slopes of Ag-4(-) and Ag-5(-), which differ for the two cases, suggests that it is the changes in fragmentation rates with internal cluster energies of Ag-4(-) and Ag-5(-) rather than conditions in the ion source that determine this behavior. Comparisons with the measurements strongly suggest that the neutral particles detected in these time domains originate from Ag-4(-) -> Ag-3(-) + Ag and Ag-5(-) -> Ag-3(-) +Ag-2 fragmentation processes.
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| 24. |
- Anderson, Emma K., 1986-
(författare)
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DESIREE: Instrumentation Developments and Hot Metal Cluster Decays
- 2019
-
Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- This thesis presents instrumentation developments and measurements performed at the Double ElectroStatic Ion Ring ExpEriment, DESIREE, at Stockholm University. DESIREE operates at cryogenic temperatures ~13 K, with very low background pressures of ~10-14mbar, allowing the observation of stored ions to long times of tens of seconds and longer.Investigations into improving the count rate capability of the DESIREE detectors are presented. Microchannel plate (MCP) detectors are used for position sensitive particle counting in the DESIREE detector assemblies. In a cryogenic environment the operational resistance of MCPs is orders of magnitude higher than at room temperature and this limits the possible count rates. Novel low-resistance MCP detectors were investigated and resulted in the replacement of the MCPs in the DESIREE detector assemblies.DESIREE was used to measure spontaneous decays of hot, small cluster anions. The decays of small silver, copper and gold cluster anions are presented and compared to statistical model calculations. An experiment that is able to measure the proportion of spontaneous decay due to fragmentation or electron detachment in dimer anions of silver and copper is presented and significant, previously overlooked, contributions from electron detachment to the decay is identified. Furthermore, measurements of the stability and decay of small carbon cluster dianions are presented. These experiments utilised the aforementioned low-resistance MCPs.
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| 25. |
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| 26. |
- Anderson, Emma K., 1986-, et al.
(författare)
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Fragmentation of and electron detachment from hot copper and silver dimer anions : A comparison
- 2023
-
Ingår i: Physical Review A: covering atomic, molecular, and optical physics and quantum information. - 2469-9926 .- 2469-9934. ; 107:6
-
Tidskriftsartikel (refereegranskat)abstract
- We measured the spontaneous decays of internally hot copper and silver dimer anions, and , stored in one of the two ion-beam storage rings of the Double Electrostatic Ion Ring Experiment (DESIREE) at Stockholm University. A coincidence detection technique was utilized enabling essentially background-free measurements of -> Cu + Cu- and -> Ag + Ag- fragmentation rates. Furthermore, the total rates of neutral decay products (monomers and dimers) were measured and the relative contributions of fragmentation and electron emission ( -> Cu2 + e- and -> Ag2 + e-) were deduced as functions of storage time. Fragmentation is completely dominant at early times. However, after about 20 ms of storage, electron emission is observed and becomes the leading decay path after 100 ms for both dimer anions. The branching ratios between fragmentation and electron emission (vibrationally assisted autodetachment processes) are very nearly the same for and Ag-2 throughout the present storage cycle of 10 seconds. This is surprising considering the difference between the electron affinities of the neutral dimers, Cu2 and Ag2, and the difference between the and the dissociation energies.
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| 27. |
- Anderson, Emma K., et al.
(författare)
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Spontaneous electron emission from hot silver dimer anions: Breakdown of the Born-Oppenheimer approximation
- 2020
-
Ingår i: Physical Review Letters. - 0031-9007 .- 1079-7114. ; 124
-
Tidskriftsartikel (refereegranskat)abstract
- We report the first experimental evidence of spontaneous electron emission from a homonuclear dimer anion through direct measurements of Ag−2 → Ag2 + e− decays on milliseconds and seconds timescales. This observation is very surprising as there is no avoided crossing between adiabatic energy curves to mediate such a process. The process is weak, yet dominates the decay signal after 100 ms when ensembles of internally hot Ag−2 ions are stored in the cryogenic ion-beam storage ring, DESIREE, for 10 s. The electron emission process is associated with an instantaneous, very large reduction of the vibrational energy of the dimer system. This represents a dramatic deviation from a Born-Oppenheimer description of dimer dynamics.
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| 28. |
- Aumayr, Friedrich, et al.
(författare)
-
Roadmap on photonic, electronic and atomic collision physics : III. Heavy particles
- 2019
-
Ingår i: Journal of Physics B. - : IOP Publishing. - 0953-4075 .- 1361-6455. ; 52:17
-
Tidskriftsartikel (refereegranskat)abstract
- We publish three Roadmaps on photonic, electronic and atomic collision physics in order to celebrate the 60th anniversary of the ICPEAC conference. Roadmap III focusses on heavy particles: with zero to relativistic speeds. Modern theoretical and experimental approaches provide detailed insight into the wide range of many-body interactions involving projectiles and targets of varying complexity ranging from simple atoms, through molecules and clusters, complex biomolecules and nanoparticles to surfaces and crystals. These developments have been driven by technological progress and future developments will expand the horizon of the systems that can be studied. This Roadmap aims at looking back along the road, explaining the evolution of the field, and looking forward, collecting nineteen contributions from leading scientists in the field.
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| 29. |
- Barklem, Paul, et al.
(författare)
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Mutual Neutralization in Li++H−/D− and Na++H−/D− Collisions : Implications of Experimental Results for Non-LTE Modeling of Stellar Spectra
- 2021
-
Ingår i: Astrophysical Journal. - : American Astronomical Society. - 0004-637X .- 1538-4357. ; 908:2
-
Tidskriftsartikel (refereegranskat)abstract
- Advances in merged-beams instruments have allowed experimental studies of the mutual neutralization (MN) processes in collisions of both Li+ and Na+ ions with D− at energies below 1 eV. These experimental results place constraints on theoretical predictions of MN processes of Li+ and Na+ with H−, important for non-LTE modeling of Li and Na spectra in late-type stars. We compare experimental results with calculations for methods typically used to calculate MN processes, namely the full quantum (FQ) approach, and asymptotic model approaches based on the linear combination of atomic orbitals (LCAO) and semiempirical (SE) methods for deriving couplings. It is found that FQ calculations compare best overall with the experiments, followed by the LCAO, and the SE approaches. The experimental results together with the theoretical calculations, allow us to investigate the effects on modeled spectra and derived abundances and their uncertainties arising from uncertainties in the MN rates. Numerical experiments in a large grid of 1D model atmospheres, and a smaller set of 3D models, indicate that neglect of MN can lead to abundance errors of up to 0.1 dex (26%) for Li at low metallicity, and 0.2 dex (58%) for Na at high metallicity, while the uncertainties in the relevant MN rates as constrained by experiments correspond to uncertainties in abundances of much less than 0.01 dex (2%). This agreement for simple atoms gives confidence in the FQ, LCAO, and SE model approaches to be able to predict MN with the accuracy required for non-LTE modeling in stellar atmospheres.
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| 30. |
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| 31. |
- Bernard, J., et al.
(författare)
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A ""tabletop"" electrostatic ion storage ring : Mini-Ring
- 2008
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Ingår i: Review of Scientific Instruments. - : AIP Publishing. - 0034-6748 .- 1089-7623. ; 79:7, s. 75109-
-
Tidskriftsartikel (refereegranskat)abstract
- We report on the design, construction, and commissioning of a novel electrostatic ion storage ring of small dimensions-in the following referred to as ""Mini-Ring."" Mini-Ring consists of four horizontal parallel-plate deflectors and two conical electrostatic mirrors. Ions are injected through the two deflectors on the injection side and off axis with respect to the conical mirrors which face each other. The first injection deflector, originally at zero voltage, is switched to its set value such that the ions after one turn follow stable trajectories of lengths of roughly 30 cm. This design reduces the number of electrodes necessary to guide the ion beam through the ring in stable orbits. The six elements (deflectors and mirrors) are placed on a common grounded plate-the tabletop. Here, we present the design, ion trajectory simulations, and results of the first test experiments demonstrating the successful room-temperature operation of Mini-Ring at background pressures of 10(-6)-10(-7) mbar.
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| 32. |
- Bernard, Jérôme, et al.
(författare)
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Efficient radiative cooling of tetracene cations C18H12+ : absolute recurrent fluorescence rates as a function of internal energy
- 2023
-
Ingår i: Physical Chemistry, Chemical Physics - PCCP. - : Royal Society of Chemistry (RSC). - 1463-9076 .- 1463-9084. ; 25:15, s. 10726-10740
-
Tidskriftsartikel (refereegranskat)abstract
- We have measured recurrent fluorescence (RF) cooling rates of internally hot tetracene cations, C18H12+, as functions of their storage times and internal energies in two different electrostatic ion-beam storage rings – the cryogenic ring DESIREE with a circumference of 8.6 meters in Stockholm and the much smaller room temperature ring Mini-Ring in Lyon, which has a circumference of 0.71 meters. The RF rates were measured to be as high as 150 to 1000 s−1 for internal energies in the 7 to 9.4 eV energy range, where we have probed the time evolution of the internal energy distribution with nanosecond laser pulses with a 1 kHz repetition rate. These RF rates are found to be significantly higher than those of previously investigated smaller PAHs such as e.g. anthracene and naphthalene, for which the lowest non-forbidden electronic excited state, the D2 state, is populated with a smaller probability by inverse internal conversion. Furthermore, the D2–D0 transition rate is smaller for these smaller molecules than for tetracene. The complementary features of the two storage rings allow for RF rate measurements in a broader internal energy range than has been possible before. The smaller sampling period of about 6 μs in Mini-Ring is ideal to study the cooling dynamics of the hotter ions that decay fast, whereas DESIREE with a sampling period of about 60 μs is better suited to study the colder ions that decay on longer timescales ranging up to hundreds of milliseconds. The excellent agreement between the two series of measurements in the region where they overlap demonstrates the complementarity of the two electrostatic ion-beam storage rings.
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| 33. |
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| 34. |
- Bernigaud, Virgile, et al.
(författare)
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Electron capture-induced dissociation of AK dipeptide dications : Influence of ion velocity, crown-ether complexation and collision gas
- 2008
-
Ingår i: International Journal of Mass Spectrometry. - : Elsevier BV. - 1387-3806 .- 1873-2798. ; 276:2-3, s. 77-81
-
Tidskriftsartikel (refereegranskat)abstract
- The fragmentation of doubly protonated AK dipeptide ions has been investigated after collisional electron transfer. Electron capture leads to three dominant channels, H loss, NH3 loss, and N–Cα bond breakage to give either c+ or z+ fragment ions. The relative importance of these channels has been explored as a function of ion velocity, the degree of complexation with crown ether, and collision gas. Our results indicate that H loss and NH3 loss are competing channels whereas the probability of N–Cα bond breakage is more or less constant.
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| 35. |
- Bull, James N., et al.
(författare)
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Ultraslow radiative cooling of Cn- (n=3-5)
- 2019
-
Ingår i: Journal of Chemical Physics. - : AIP Publishing. - 0021-9606 .- 1089-7690. ; 151:11
-
Tidskriftsartikel (refereegranskat)abstract
- Ultraslow radiative cooling lifetimes and adiabatic detachment energies for three astrochemically relevant anions, Cn- (n = 3-5), are measured using the Double ElectroStatic Ion Ring ExpEriment (DESIREE) infrastructure at Stockholm University. DESIREE maintains a background pressure of approximate to 10(-14) mbar and temperature of approximate to 13 K, allowing storage of mass-selected ions for hours and providing conditions coined a molecular cloud in a box. Here, we construct two-dimensional (2D) photodetachment spectra for the target anions by recording photodetachment signal as a function of irradiation wavelength and ion storage time (seconds to minute time scale). Ion cooling lifetimes, which are associated with infrared radiative emission, are extracted from the 2D photodetachment spectrum for each ion by tracking the disappearance of vibrational hot-band signal with ion storage time, giving 1e cooling lifetimes of 3.1 +/- 0.1 s (C3-), 6.8 +/- 0.5 s (C4-), and 24 +/- 5 s (C5-). Fits of the photodetachment spectra for cold ions, i.e., those stored for at least 30 s, provide adiabatic detachment energies in good agreement with values from laser photoelectron spectroscopy on jet-cooled anions, confirming that radiative cooling has occurred in DESIREE. Ion cooling lifetimes are simulated using a simple harmonic cascade model, finding good agreement with experiment and providing a mode-by-mode understanding of the radiative cooling properties. The 2D photodetachment strategy and radiative cooling modeling developed in this study could be applied to investigate the ultraslow cooling dynamics of a wide range of molecular anions.
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| 36. |
- Bäckström, Erik, 1983-, et al.
(författare)
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Storing keV negative ions for an hour : The lifetime of the metastable 2P1/2 level in 32S−
- 2015
-
Ingår i: Physical Review Letters. - 0031-9007 .- 1079-7114. ; 114:14
-
Tidskriftsartikel (refereegranskat)abstract
- We use a novel electrostatic ion storage ring to measure the radiative lifetime of the upper level in the 3p 5 P 2 o 1/2 →3p 5 P 2 o 3/2 spontaneous radiative decay in S − 32 to be 503±54 sec . This is by orders of magnitude the longest lifetime ever measured in a negatively charged ion. Cryogenic cooling of the storage ring gives a residual-gas pressure of a few times 10 −14 mbar at 13 K and storage of 10 keV sulfur anions for more than an hour. Our experimental results differ by 1.3σ from the only available theoretical prediction.
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| 37. |
- Cederquist, Kristina, et al.
(författare)
-
A population based cohort study of patients with multiple colon and endometrial cancer: correlation of microsatellite instability (MSI) staus, age at diagnosis and cancer risk
- 2001
-
Ingår i: International Journal of Cancer. - 0020-7136 .- 1097-0215. ; 91:4, s. 486-491
-
Tidskriftsartikel (refereegranskat)abstract
- Hereditary non-polyposis colorectal cancer, HNPCC, is an autosomal dominant condition predisposing to cancers of primarily the colorectum and the endometrium. The aim of our study was to identify persons at a high risk of hereditary colorectal cancer and to estimate their risk of colon and other HNPCC-associated tumours. Family histories of cancer were obtained on 89 persons with double primary (DP) cancers of the colon and the endometrium. The cancer risks in their 649 first-degree-relatives (FDR) were analysed. The microsatellite instability (MSI) status of the tumour of the proband was also analysed and the cancer risks were estimated in relation to MSI status and age at diagnosis in the proband (over or under 50 years). The overall standardised incidence ratio (SIR) was 1.69 (95% CI; 1.39-2.03). In the =50-year-old cohort the SIR was 2.67 (95% CI; 2.08-3.38). Colon, rectal and uterus cancer exhibited significantly increased risks. This risk was further increased in the =50-year-old MSI positive families. Several =50-year-old MSI negative HNPCC-like families with increased risks were also identified. In conclusion a FDR to a person with a DP cancer of the colorectum or the colon/endometrium have a significantly increased risk of having a colorectal or other HNPCC-associated cancers if the proband is diagnosed with one of the cancers before age 50. These families are candidates for genetic counselling and colorectal screening programmes. Mutations in mismatch repair genes can explain some of the increased risk in these families, but mutations in MSI negative families are probably due to other colon cancer susceptibility genes not yet described. Copyright 2001 Wiley-Liss, Inc.
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| 38. |
- Cederquist, Kristina, 1971-
(författare)
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Genetic and epidemiological studies of hereditary colorectal cancer
- 2005
-
Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- Lynch syndrome (Hereditary Nonpolyposis Colorectal Cancer, HNPCC) is the most common hereditary syndrome predisposing to colorectal cancer, accounting for 1-3% of all colorectal cancer. This multi-organ cancer predisposition syndrome is caused by mutations in the mismatch repair (MMR) genes, especially MLH1 and MSH2, and to lesser extents MSH6 and PMS2, which lead to widespread genetic instability and thus microsatellite instability (MSI). Hereditary cancer often manifests in two or more tumours in a single individual; 35-40% of Lynch syndrome patients have synchronous or metachronous tumours of the two major Lynch syndrome-related cancers: colorectal and endometrial. The main purposes of the work underlying this thesis were to identify persons at risk of Lynch syndrome or other types of hereditary colorectal cancer, to estimate the cancer risks associated with these predispositions and to identify the underlying genetic causes. A population-based cohort of 78 persons with double primary colorectal or colorectal and endometrial cancer was identified. Cancer risks in their 649 first-degree relatives were estimated in relation to tumour MSI status (positive or negative) and age at diagnosis (before or after 50 years of age) in the probands. The overall standardised incidence ratio was 1.69 (95% CI; 1.39-2.03). The highest risks for Lynch syndrome-associated cancers: (colorectal, endometrial, ovarian and gastric) were found in families with young MSI-positive probands, likely representing Lynch syndrome families. Importantly, no overall risk was found in families with old probands, irrespective of MSI status. Blood samples were available from 24 MSI-positive patients for mutation screening of MLH1, MSH2 and MSH6. Sequence variants or rearrangements predicted to affect protein function were found in 16 patients. Six novel variants were found: two large rearrangements, two truncating and two missense mutations. The missense mutations were found to segregate in the families. Studies of allele frequencies, MSI and loss of immunostaning in tumours from family members further supports the hypothesis that these missense changes play a role in Lynch syndrome, as do the non-conservative nature and evolutionary conservation of the amino acid exchanges. Five families had mutations in MLH1, five in MSH2, and six in MSH6. The unexpectedly large impact of MSH6 was in genealogical studies shown to be due to a founder effect. Cumulative risk studies showed that the MSH6 families, despite their late age of onset, have a high lifetime risk for all Lynch syndrome-related cancers, significantly higher in women (89% by age 80 years) than in men (69%). The gender differences are in part due to high endometrial (70%) and ovarian cancer risk (33%) in addition to the high colorectal cancer risk (60%). These findings are of great importance for counselling and surveillance of families with MSH6 mutations. Finally, in a large family with MSI-negative hereditary colorectal cancer for which the MMR genes and APC had been excluded as possible causes, a genome-wide linkage analysis was performed, resulting in a suggested linkage to chromosome 7. Conclusions: Relatives of probands with MSI-positive, double primary colorectal and endometrial cancer diagnosed before the age of 50 years have significantly increased risks of Lynch syndrome-related cancers. MSH6 mutations, which have unusually high impact in this study population due to a founder effect, confer high cumulative risks of cancer despite the generally late age of onset.
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| 39. |
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| 40. |
- Cederquist, Kristina, et al.
(författare)
-
Mutation analysis of the MLH1, MSH2 and MSH6 genes in patients with double primary cancers of the colorectum and the endometrium: a population-based study in northern Sweden
- 2004
-
Ingår i: International Journal of Cancer. - : Wiley. - 0020-7136 .- 1097-0215. ; 109:3, s. 370-376
-
Tidskriftsartikel (refereegranskat)abstract
- Hereditary nonpolyposis colorectal cancer (HNPCC) is an autosomal dominant disorder that predisposes to predominantly colorectal and endometrial cancers due to germline mutations in DNA mismatch repair genes, mainly MLH1, MSH2 and in families with excess endometrial cancer also MSH6. In this population-based study, we analysed the mutation spectrum of the MLH1, MSH2 and MSH6 genes in a cohort of patients with microsatellite unstable double primary tumours of the colorectum and the endometrium by PCR, DHPLC and sequencing. Fourteen of the 23 patients (61%) had sequence variants in MLH1, MSH2 or MSH6 that likely affect the protein function. A majority (10/14) of the mutations was found among probands diagnosed before age 50. Five of the mutations (36%) were located in MLH1, 3 (21%) in MSH2 and 6 (43%) in MSH6. MSH6 seem to have larger impact in our population than in other populations, due to a founder effect since all of the MSH6 families originate from the same geographical area. MSH6 mutation carriers have later age of onset of both colorectal cancer (62 vs. 51 years) and endometrial cancer (58 vs. 48 years) and a larger proportion of endometrial cancer than MLH1 or MSH2 mutation carriers. We can conclude that patients with microsatellite unstable double primary cancers of the colorectum and the endometrium have a very high risk of carrying a mutation not only in MLH1 or MSH2 but also in MSH6, especially if they get their first cancer diagnosis before the age of 50. Copyright 2004 Wiley-Liss, Inc.
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| 41. |
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| 42. |
- Cederquist, Kristina, et al.
(författare)
-
Two Swedish founder MSH6 mutations, one nonsense and one missense, conferring high cumulative risk of Lynch syndrome.
- 2005
-
Ingår i: Clinical Genetics. - : Wiley. - 0009-9163 .- 1399-0004. ; 68:6, s. 533-541
-
Tidskriftsartikel (refereegranskat)abstract
- Lynch syndrome, or hereditary non-polyposis colorectal cancer (HNPCC), is a cancer susceptibility syndrome caused by germline mutations in mismatch-repair genes, predominantly MLH1, MSH2 and MSH6. A majority of the mutations reported are truncating, but for MSH6, missense mutations constitute over one third. Few have been proven pathogenic in functional studies or shown to segregate in families. In this study, we show segregation of the putative pathogenic MSH6 missense mutation c.1346T>C p.Leu449Pro with microsatellite instability-high Lynch syndrome-related tumours lacking MSH6 expression in a large 17th century pedigree. Another large family with the MSH6 nonsense c.2931C>G, p.Tyr977X mutation is similar in tumour spectra, age of onset and cumulative risk. These MSH6 families, despite their late age of onset, have a high lifetime risk of all Lynch syndrome-related cancers, significantly higher in women (89% by age 80) than in men (69%). The gender differences are in part explained by high endometrial (70%) and ovarian (33%) cancer risks added upon the high colorectal cancer risk (60%). The several occurrences of breast cancer are not due to the MSH6 mutations. These findings are of great importance for counselling, management and surveillance of families with MSH6 mutations.
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| 43. |
- Chartkunchand, Kiattichart C., et al.
(författare)
-
Dianion diagnostics in DESIREE : High-sensitivity detection of C-n(2-) from a sputter ion source
- 2018
-
Ingår i: Review of Scientific Instruments. - : AIP Publishing. - 0034-6748 .- 1089-7623. ; 89:3
-
Tidskriftsartikel (refereegranskat)abstract
- A sputter ion source with a solid graphite target has been used to produce dianions with a focus on carbon cluster dianions, C-n(2-), with n = 7-24. Singly and doubly charged anions from the source were accelerated together to kinetic energies of 10 keV per atomic unit of charge and injected into one of the cryogenic (13 K) ion-beam storage rings of the Double ElectroStatic Ion Ring Experiment facility at Stockholm University. Spontaneous decay of internally hot C-n(2-) dianions injected into the ring yielded C-n(2-) anions with kinetic energies of 20 keV, which were counted with a microchannel plate detector. Mass spectra produced by scanning the magnetic field of a 90 degrees analyzing magnet on the ion injection line reflect the production of internally hot C-7(2-) - C-24(2-) dianions with lifetimes in the range of tens of microseconds to milliseconds. In spite of the high sensitivity of this method, no conclusive evidence of C-6(2-) was found while there was a clear C-7(2-) signal with the expected isotopic distribution. This is consistent with earlier experimental studies and with theoretical predictions. An upper limit is deduced for a C-6(2-) signal that is two orders-of-magnitude smaller than that for C-7(2-). In addition, CnO2- and CnCu2- dianions were detected.
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| 44. |
- Chartkunchand, Kiattichart C., et al.
(författare)
-
Radiative lifetimes of the bound excited states of Pt-
- 2016
-
Ingår i: Physical Review A - Atomic, Molecular, and Optical Physics. - 1050-2947 .- 1094-1622. ; 94:3
-
Tidskriftsartikel (refereegranskat)abstract
- © 2016 American Physical Society.The intrinsic radiative lifetimes of the 5d106sS1/22 and 5d96s2 D3/22 bound excited states in the platinum anion Pt- have been studied at cryogenic temperatures at the Double ElectroStatic Ion Ring Experiment (DESIREE) facility at Stockholm University. The intrinsic lifetime of the higher-lying 5d106s S1/22 state was measured to be 2.54±0.10s, while only a lifetime in the range of 50-200 ms could be estimated for the 5d96s2 D3/22 fine-structure level. The storage lifetime of the Pt- ion beam was measured to be a little over 15 min at a ring temperature of 13K. The present study reports the lifetime of an atomic negative ion in an excited bound state with an electron configuration different from that of the ground state.
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| 45. |
- Chen, Tao, et al.
(författare)
-
Absolute fragmentation cross sections in atom-molecule collisions : Scaling laws for non-statistical fragmentation of polycyclic aromatic hydrocarbon molecules
- 2014
-
Ingår i: Journal of Chemical Physics. - : AIP Publishing. - 0021-9606 .- 1089-7690. ; 140:22
-
Tidskriftsartikel (refereegranskat)abstract
- We present scaling laws for absolute cross sections for non-statistical fragmentation in collisions between Polycyclic Aromatic Hydrocarbons (PAH/PAH(+)) and hydrogen or helium atoms with kinetic energies ranging from 50 eV to 10 keV. Further, we calculate the total fragmentation cross sections (including statistical fragmentation) for 110 eV PAH/PAH(+) + He collisions, and show that they compare well with experimental results. We demonstrate that non-statistical fragmentation becomes dominant for large PAHs and that it yields highly reactive fragments forming strong covalent bonds with atoms (H and N) and molecules (C6H5). Thus nonstatistical fragmentation may be an effective initial step in the formation of, e. g., Polycyclic Aromatic Nitrogen Heterocycles (PANHs). This relates to recent discussions on the evolution of PAHNs in space and the reactivities of defect graphene structures.
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| 46. |
- Chen, Tao, et al.
(författare)
-
Formation of H2 from internally heated polycyclic aromatic hydrocarbons : Excitation energy dependence
- 2015
-
Ingår i: Journal of Chemical Physics. - : AIP Publishing. - 0021-9606 .- 1089-7690. ; 142:14
-
Tidskriftsartikel (refereegranskat)abstract
- We have investigated the effectiveness of molecular hydrogen (H-2) formation from Polycyclic Aromatic Hydrocarbons (PAHs) which are internally heated by collisions with keV ions. The present and earlier experimental results are analyzed in view of molecular structure calculations and a simple collision model. We estimate that H-2 formation becomes important for internal PAH temperatures exceeding about 2200 K, regardless of the PAH size and the excitation agent. This suggests that keV ions may effectively induce such reactions, while they are unlikely due to, e.g., absorption of single photons with energies below the Lyman limit. The present analysis also suggests that H-2 emission is correlated with multi-fragmentation processes, which means that the [PAH-2H](+) peak intensities in the mass spectra may not be used for estimating H-2-formation rates.
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| 47. |
- Chen, Tao, 1984-
(författare)
-
Ions colliding with molecules and molecular clusters : fragmentation and growth processes
- 2015
-
Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- In this work we will discuss fragmentation and molecular growth processes in collisions of Polycyclic Aromatic Hydrocarbon (PAH) molecules, fullerenes, or their clusters with atoms or atomic ions. Simple collision models as well as molecular structure calculations are used to aid the interpretations of the present and other experimental results. Fragmentation features at center-of-mass collision energies around 10 keV are dominated by interactions between the fast ion/atom and the electron cloud in the molecules/clusters (electronic stopping processes). This electronic excitation energy is rapidly distributed on the vibrational degrees of freedom of the molecule or of the molecules in a cluster and may result in fragmentation. Here, the fragmentation is statistical and favors the lowest-energy dissociation channels which are losses of intact molecules from clusters, H- and C2H2-losses from isolated PAHs, and C2-loss from fullerene monomers. We will also discuss the possibility of formation of molecular H2 direct from native PAHs which reach high enough energies when interacting with ions, electrons, or photons.For the experiments at lower center of mass collision energies (~100 eV) a single atom may be knocked out in close atom-atom interaction. Such non-statistical fragmentation are due to nuclear stopping processes and gives highly reactive fragments which may form covalent bonds with other molecules in a cluster on very short time scales (picoseconds). This process may be important when considering the formation of new species. For collision between 12 keV Ar2+ and clusters of pyrene (C16H10) molecules, new molecules, e.g. C17H10+, C30H18+, C31H19+, etc are detected. We also observe molecular fusion processes for He and Ar ions colliding with clusters of C60 molecules. These and related molecular fusion processes may play a key role for understanding molecular growth processes under certain astrophysical conditions.
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| 48. |
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| 49. |
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| 50. |
- da Silva, Humberto, Jr., et al.
(författare)
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Multiple electron capture, excitation, and fragmentation in C6+-C-60 collisions
- 2014
-
Ingår i: Physical Review A. Atomic, Molecular, and Optical Physics. - 1050-2947 .- 1094-1622. ; 90:3, s. 032701-
-
Tidskriftsartikel (refereegranskat)abstract
- We present experimental and theoretical results on single- and multiple-electron capture, and fragmentation, in C6+ + C-60 collisions at velocities in the v(col) = 0.05 - 0.4 a.u. range. We use time-of-flight mass spectrometry and coincidence detection of charged fragments to separate pure target ionization from processes in which the C-60 target is both ionized and fragmented. The coincidence technique allows us to identify different types of fragmentation processes such as C-60(q+) -> C-58(q+) + C-2 and C-60(q+) -> C-58((q-1)+) + C-2(+). A quasimolecular approach is employed to calculate charge transfer and target excitation cross sections. First-order time-dependent perturbation and statistical methods are used to treat the postcollisional processes: the calculated rate constants for C-2 and C-2(+) emission from the excited and charged fullerene are then used to evaluate the fragmentation dynamics. We show that the target ionization cross section decreases with the induced target charge state and the impact energy. C-2 emission from C-60(q+) is found to dominate when q <= 2 while C-2(+) emission dominates when q >= 5, in agreement with the present and previous experimental results.
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