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High-precision measurements of the electron affinities (EA) of the three stable isotopes of silicon, $^{28}$Si, $^{29}$Si and $^{30}$Si, have been performed at the cryogenic electrostatic ion-beam storage ring DESIREE. The quantum states of the ions were manipulated using laser depletion, and the ions were photodetached by laser photodetachment threshold spectroscopy. These EA values are the first reported for $^{29}$Si$^-$ and $^{30}$Si$^-$ and provide a reduced uncertainty for $^{28}$Si$^-$. The resulting EAs are $EA(^{28}$Si$) = 1.38952201(17)$ eV, $EA(^{29}$Si$) = 1.38952172(12)$ eV and $EA(^{29}$Si$) = 1.38952078(12)$ eV, with the corresponding isotope shifts $IS(^{29-28}$Si$) = 0.29(16)$ micro eV and $IS(^{30-28}$Si$) = 1.23(16) $ micro eV. In addition to these measurements, the resolution and signal-to-background level was sufficient to reveal the hyperfine structure splitting in the $^{29}$Si$^-$ isotope, which we report to be $1.8(4) micro eV.

We report the first experimental evidence of spontaneous electron emission from a homonuclear dimer anion through direct measurements of $\rm{Ag}_2^- \rightarrow \rm{Ag}_2 + \rm{e}^-$ decays on milliseconds and seconds time scales. This observation is very surprising as there is no avoided crossing between adiabatic energy curves to mediate such a process. The process is weak but 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 seconds. 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.

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 ($\sim10^{-14}$) and cryogenic (13 K) operation of DESIREE. The yield of neutral particles from stored beams of Ag$_{6}$ and Ag$_{7}$ anions were measured for 100 milliseconds and were found to follow single power law behaviour with millisecond time scale exponential cut-offs. The Ag$_{4}$ and Ag$_{5}$ anions were stored for 60 seconds 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 determines this behavior. Comparisons with the measurements strongly suggest that the neutral particles detected in these time domains originate from Ag$_{4} \rightarrow$ Ag$_{3}+$ Ag and Ag$_{5}\rightarrow$ Ag$_{3}+$ Ag$_{2}$ fragmentation processes.

We give a detailed description of an electrospray ion source test bench and a single-pass setup for ion fragmentation studies at the DESIREE infrastructure at Stockholm University. This arrangement allows for collision induced dissociation experiments at center-of-mass energies between 10 eV and 1 keV. Charged fragment 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., Comment: 13 pages, 15 figures. Instrumentation paper

We have measured total absolute cross sections for the Mutual Neutralization (MN) of O- with O+/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 multi-channel 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., Comment: 5 pages, 4 figures

We have measured the threshold center-of-mass kinetic energy for knocking out a single carbon atom from C$_{60}^-$ in collisions with He. Combining this experimental result with classical molecular dynamics simulations, we determine a semi-empirical value of 24.1$\pm$0.5~eV for the threshold displacement energy, the energy needed to remove a single carbon atom from the C$_{60}$ cage. We report the first observation of an endohedral complex with an odd number of carbon atoms, He@C$_{59}^-$, and discuss its formation and decay mechanisms.

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 DESIREE (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 eV or 1.45 eV photons after 46 milliseconds of storage.

The intrinsic radiative lifetimes of the $5d^{10}6s$ $^{2}\text{S}_{1/2}$ and $5d^{9}6s^{2}$ $^{2}\text{D}_{3/2}$ bound excited states in the platinum anion $\text{Pt}^{-}$ 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 $5d^{10}6s$ $^{2}\text{S}_{1/2}$ state was measurement to be 2.54$\pm$0.10 s, while only a lifetime in the range of 50 - 200 ms could be estimated for the $5d^{9}6s^{2}$ $^{2}\text{D}_{3/2}$ fine-structure level. The storage lifetime of the $\text{Pt}^{-}$ ion beam was measured to be a little over 15 minutes 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., Comment: 6 pages, 5 figures

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 (C$_n^-$, $n=1,2,3,4$) 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 C$_2^-$ molecular anions we measure the residual-gas limited beam storage lifetime to be 448 s $\pm$ 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. %The latter effect becomes insignificant after longer storage times of typically 100-150 seconds and we then observe a constant decay rate due to residual-gas collisions.

A sputter ion source with a solid graphite target has been used to produce dianions with a focus on carbon cluster dianions, $\text{C}_{n}^{2-}$, 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 $\text{C}_{n}^{2-}$ dianions injected into the ring yielded $\text{C}^{-}$ 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 $90^{\circ}$ analyzing magnet on the ion injection line reflect the production of internally hot $\text{C}_{7}^{2-}-\text{C}_{24}^{2-}$ 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 $\text{C}_{6}^{2-}$ was found while there was a clear $\text{C}_{7}^{2-}$ signal with the expect isotopic distribution. An upper limit is deduced for a $\text{C}_{6}^{2-}$ signal that is two orders-of-magnitue smaller than that for $\text{C}_{7}^{2-}$. In addition, $\text{C}_{n}\text{O}^{2-}$ and $\text{CsCu}^{2-}$ dianions were detected., Comment: 6 pages, 6 figures

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$\pm$0.2 K with 94.9$\pm$0.3 % of the ions in the rotational ground state. This is consistent with the storage ring temperature of 13.5$\pm$0.5 K as measured with eight silicon diodes, but in contrast to all earlier studies in cryogenic traps and rings where the rotational temperatures were always much higher than those of the storage devices at their lowest temperatures. Furthermore, we actively modify the rotational distribution through selective photodetachment to produce an OH$^-$ beam where 99.1$\pm$0.1 % of approximately one million stored ions are in the $J$=0 rotational ground state.

We have investigated the photo-stability of pristine and super-hydrogenated pyrene cations C$_{16}$H$_{10+m}^+, m = 0,6, \mathrm{\ or\ } 16$) by means of gas-phase action spectroscopy. Optical absorption spectra and photo-induced 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 (C$_{16}$H$_{10}^+$) requires absorption of three photons of energy just below 3 eV, whereas super-hydrogenated hexahydropyrene (C$_{16}$H$_{16}^+$) must absorb two such photons and fully hydrogenated hexadecahydropyrene (C$_{16}$H$_{26}^+$) 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., Comment: 6 pages, 4 figures, accepted in The Astrophysical Journal

We have measured absolute cross sections for ultrafast (fs) single-carbon knockout from Polycyclic Aromatic Hydrocarbon (PAH) cations as functions of He-PAH center-of-mass collision energy in the range 10-200 eV. Classical Molecular Dynamics (MD) simulations cover this range and extend up to 10$^5$ eV. The shapes of the knockout cross sections are well described by a simple analytical expression yielding experimental and MD threshold energies of $E_{th}^{Exp}=32.5\pm 0.4$ eV and $E_{th}^{MD}=41.0\pm 0.3$ eV, respectively. These are the first measurements of knockout threshold energies for molecules isolated \emph{in vacuo}. We further deduce semi-empirical (SE) and MD displacement energies --- \emph{i.e.} the energy transfers to the PAH molecules at the threshold energies for knockout --- of $T_{disp}^{SE}=23.3\pm 0.3$ eV and $T_{disp}^{MD}=27.0\pm 0.3$ eV. The semi-empirical results compare favorably with measured displacement energies for graphene $T_{disp}=23.6$ eV [Meyer \emph{et al.} Phys. Rev Lett. \textbf{108} 196102 (2012) and \textbf{110} 239902 (2013)].

The intrinsic lifetime of the upper level in the bound-bound 3d$^9$4s$^2$ $^2$D$_{3/2}$ $\rightarrow$ 3d$^9$4s$^2$ $^2$D$_{5/2}$ radiative transition in Ni$^-$ was measured to be 15.1 $\pm$ 0.4 s. The experiment was performed at cryogenic temperatures in one of the ion-beam storage rings of the DESIREE (Double ElectroStatic Ion Ring Experiment) facility at Stockholm University. The storage lifetime of the Ni$^-$ ion-beam was measured to be close to five minutes at a ring temperature of 13 K., Comment: 12 pages, 5 figures