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In this paper, we give a detailed description of an electrospray ion source test bench and a single-pass setup for ion fragmentation studies at the Double ElectroStatic Ion Ring ExpEriment infrastructure at Stockholm University. This arrangement allows for collision-induced dissociation experiments at the center-of-mass energies between 10 eV and 1 keV. Charged fragments are analyzed with respect to their kinetic energies (masses) by means of an electrostatic energy analyzer with a wide angular acceptance and adjustable energy resolution.

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.

We have measured total absolute cross sections for the mutual neutralization (MN) of O- with O+ and N+. A fine resolution (of about 50 meV) in the kinetic energy spectra of the product neutral atoms allows unique identification of the atomic states participating in the mutual neutralization process. Cross sections and branching ratios have also been calculated down to 1 meV center-of-mass collision energy for these two systems, with a multichannel Landau-Zener model and an asymptotic method for the ionic-covalent coupling matrix elements. The importance of two-electron processes in one-electron transfer is demonstrated by the dominant contribution of a core-excited configuration of the nitrogen atom in N+ + O- collisions. This effect is partially accounted for by introducing configuration mixing in the evaluation of coupling matrix elements.

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.

We have measured the spontaneous neutral particle emission from copper-cluster anions ( Cu-n(-), n = 3-6) stored at cryogenic temperatures in one of the electrostatic ion storage rings of the Double ElectroStatic Ion Ring ExpEriment facility at Stockholm University. The measured rate of emission from the stored Cu-3(-) ions follows a single power-law decay for about 1 ms but then decreases much more rapidly with time. The latter behavior may be due to a decrease in the density of available final states in Cu-3 as the excitation energies of the decaying ions approach the electron detachment threshold. The emissions from Cu-4(-), Cu-5(-), and Cu-6(-) are well described by sums of two power laws that are quenched by radiative cooling of the stored ions with characteristic times between a few and hundreds of milliseconds. We relate these two-component behaviors to populations of stored ions with higher and lower angular momenta. In a separate experiment, we studied the laser-induced decay of Cu-6(-) ions that were excited by 1.13- or 1.45-eV photons after 46 ms of storage.

We have studied collisions between tetraphenylporphyrin cations and He or Ne at center-of-mass energies in the range 50-110 eV. The experimental results were interpreted in view of density functional theory calculations of dissociation energies and classical molecular dynamics simulations of how the molecules respond to the He/Ne impact. We demonstrate that prompt atom knockout strongly contributes to the total destruction cross sections. Such impulse driven processes typically yield highly reactive fragments and are expected to be important for collisions with any molecular system in this collision energy range, but have earlier been very difficult to isolate for biomolecules.

We apply near-threshold laser photodetachment to characterize the rotational quantum level distribution of OH- ions stored in the cryogenic ion-beam storage ring DESIREE at Stockholm University. We find that the stored ions relax to a rotational temperature of 13.4 +/- 0.2 K with 94.9 +/- 0.3% of the ions in the rotational ground state. This is consistent with the storage ring temperature of 13.5 +/- 0.5 K as measured with eight silicon diodes but in contrast to all earlier studies in cryogenic traps and rings where the rotational temperatures were always much higher than those of the storage devices at their lowest temperatures. Furthermore, we actively modify the rotational distribution through selective photodetachment to produce an OH- beam where 99.1 +/- 0.1% of approximately one million stored ions are in the J = 0 rotational ground state. We measure the intrinsic lifetime of the J = 1 rotational level to be 145 +/- 28 s.

The intrinsic lifetime of the upper level in the bound-bound 3d(9) 4s(2) D-2(3/2) -> 3d(9) 4s(2) D-2(5/2) radiative transition in Ni- was measured to be 15.1 +/- 0.4 s. The experiment was performed at cryogenic temperatures in one of the ion-beam storage rings of the Double ElectroStatic Ion Ring ExpEriment facility at Stockholm University. The storage lifetime of the Ni- ion beam was measured to be close to 5 min at a ring temperature of 13 K.

The intrinsic radiative lifetimes of the 5d(10)6s(2)S(1/2) and 5d(9)6s(2) D-2(3/2) 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 5d(10)6s S-2(1/2) state was measured to be 2.54 +/- 0.10 s, while only a lifetime in the range of 50-200 ms could be estimated for the 5d(9)6s(2) D-2(3/2) 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 13 K. 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.

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.

The exploration of the unique properties of stored and cooled beams of highly-charged ions as provided by heavy-ion storage rings has opened novel and fascinating research opportunities in the realm of atomic and nuclear physics research. Since the late 1980s, pioneering work has been performed at the CRYRING at Stockholm (Abrahamsson et al. 1993) and at the Test Storage Ring (TSR) at Heidelberg (Baumann et al. 1988). For the heaviest ions in the highest charge-states, a real quantum jump was achieved in the early 1990s by the commissioning of the Experimental Storage Ring (ESR) at GSI Helmholtzzentrum für Schwerionenforschung (GSI) in Darmstadt (Franzke 1987) where challenging experiments on the electron dynamics in the strong field regime as well as nuclear physics studies on exotic nuclei and at the borderline to atomic physics were performed. Meanwhile also at Lanzhou a heavy-ion storage ring has been taken in operation, exploiting the unique research opportunities in particular for medium-heavy ions and exotic nuclei (Xia et al. 2002).

We have observed significant differences in the fragmentation patterns of isomeric Polycyclic Aromatic Hydrocarbon (PAH) cations following collisions with helium atoms at center-of-mass energies around 100 eV. This is in contrast to the situation at other collision energies or in photo-absorption experiments where isomeric effects are very weak and where the lowest-energy dissociation channels (H- and C2H2-loss) domihate in statistical fragmentation processes. In the 100 eV range, non-statistical fragmentation also competes and is uniquely linked to losses of single carbon atoms (CHx-losses). We find that such CHx-losses are correlated with the ionic ground state energy within a given group of isomers. We present results for three C16H10+, four C18H12+ and five C20H12+ isomers colliding with He.

We have measured absolute cross sections for ultrafast (femtosecond) single-carbon knockout from polycyclic aromatic hydrocarbon (PAR) cations as functions of He-PAR center-of-mass collision energy in the 10-200 eV range. Classical molecular dynamics (MD) simulations cover this range and extend up to 105 eV. The shapes of the knockout cross sections are well-described by a simple analytical expression yielding experimental and MD threshold energies of E-th(Exp) = 32.5 +/- 0.4 eV and E-th(MD) = 41.0 +/- 0.3 eV, respectively. These are the first measurements of knockout threshold energies for molecules isolated in vacuo. We further deduce semiempirical (SE) and MD displacement energies, i.e., the energy transfers to the PAH molecules at the threshold energies for knockout, of T-disp(SE) = 23.3 +/- 0.3 eV and T-disp(MD) = 27.0 +/- 0.3 eV. The semiempirical results compare favorably with measured displacement energies for graphene (T-disp = 23.6 eV).

A recent study of soft x-ray absorption in native and hydrogenated coronene cations, C24H12+m + m = 0-7, led to the conclusion that additional hydrogen atoms protect (interstellar) polycyclic aromatic hydrocarbon (PAH) molecules from fragmentation [Reitsma et al., Phys. Rev. Lett. 113, 053002 (2014)]. The present experiment with collisions between fast (30-200 eV) He atoms and pyrene (C16H10+m +, m = 0, 6, and 16) and simulations without reference to the excitation method suggests the opposite. We find that the absolute carbon-backbone fragmentation cross section does not decrease but increases with the degree of hydrogenation for pyrene molecules.

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.

Here we will briefly describe the commissioning of the Double ElectroStatic Ion Ring ExpEriment (DESIREE) facility at Stockholm University, Sweden. This device uses purely electrostatic focussing and deflection elements and allows ion beams of opposite charge to be confined under extreme high vacuum and cryogenic conditions in separate rings and then merged over a common straight section. This apparatus allows for studies of interactions between cations and anions at very low and well-defined centre-of-mass energies (down to a few meV) and at very low internal temperatures (down to a few K)., AuthorCount:35

We have studied the fragmentation of the singly protonated L- and D-forms of enantiomerically pure phenylalanine (Phe), tryptophan (Trp), and methionine (Met) in high-energy collisions with chiral and achiral gas targets. (S)-(+)-2-butanol, racemic (+/-)-2-butanol, and argon were used as target gases. At center-of-mass frame collision energy of I key, it was found that all of the ions exhibit common fragmentation pathways which are independent of target chirality. For all projectile ions, the elimination of NH3 and H2O + CO were found to be the main reaction channels. The observed fragmentation patterns were dominated by statistically driven processes. The energy deposited into the ions was found to be sufficient to yield multiple fragment ions, which arise from decomposition via various competitive reaction pathways.

A significant number of electrostatic ion-storage rings have been built since the late 1990s or are currently in their construction or commisioning phases. In this short contribution, we attempt to supply an overview of these different facilities, while we also mention a selection of the electrostatic ion-beam traps that has been developed through the same time period and by some of the same research groups.