We measured the spontaneous and photoinduced decays of anionic gold clusters, , with sizes ranging from 𝑁=2 to 13 and 15. After production in a sputter ion source, the size-selected clusters were stored in the cryogenic electrostatic ion-beam storage ring DESIREE, and their neutralization decays were measured for storage times between 0.1 and 100 s. The dimer was observed to decay by electron emission in parallel to neutral atom emission at long times, implying a breakdown of the Born-Oppenheimer approximation, analogous to the behavior of copper and silver dimers. Radiative cooling is observed for all other cluster sizes. The decays of clusters 𝑁=3,6,8–13,15 show only a single radiative cooling time. For 𝑁=6–13 the cooling times have a strong odd-even oscillation with an amplitude that decrease with cluster size and with the even 𝑁 having the faster cooling. We compare our results with previous measurements of radiative cooling rates of the corresponding cationic gold clusters, , which also show an odd-even effect with a similar oscillation amplitude but at orders of magnitude shorter timescales and out of phase with the anions. The tetramer and pentamer both show two cooling times, which we tentatively ascribe to different structural forms at different ranges of high angular momenta of the ions in the and beams. For , the shape of the decay curve suggests that the cluster cools by emission of low-energy photons. The calculated limit on photon energies strongly suggests that cooling is by vibrational transitions in this case. For , time-resolved studies of photoinduced decays were performed to track the evolution of the internal energy distribution. We conclude that the radiative cooling is dominated by sequences of vibrational transitions in the IR. The laser-enhanced neutralization rate of was exponential, in contrast to its spontaneous decay rate, indicating that the cluster had already been cooled to a very narrow internal energy distribution at 120 ms as the total (integrated) laser-enhanced intensity was independent of the laser firing time at later times. The unimolecular rate constants decreased from 500 s⁻¹ when laser excited at 0.12 s to 40 s⁻¹ when laser excited at 0.62 s.

This thesis presents experimental studies of mutual-neutralization reactions between H^- and the cations ⁷Li⁺, ¹⁶O⁺, ¹²C⁺ and ¹⁴N⁺ at the double electrostatic ion-beam storage ring DESIREE. By overlapping two keV ion beams, with corresponding speeds of ca. 1000 km/s, and matching their velocities with applied electric fields, the center-of-mass collision energies are reduced to a few tens of meV. Time- and position-sensitive detectors allow the measurement of the  separation of the two formed neutral products, which depends on the kinetic-energy release in the charge-transfer reaction. The branching fractions into the different quantum states are extracted by binning or modelling of the measured product-separation distributions.

Due to the difficulty of merged-beams experiments with high mass ratio between the ions, ¹H^- is often replaced with ²H^-. We were able to merge beams with a mass ratio of up to 16 between the ions, which allowed us to use ¹H^- in all studies presented here. For H^-+⁷Li⁺ and H^-+¹⁶O⁺, we included both hydrogen isotopes, and found a significant isotope effect. The lighter hydrogen isotope leads to an increased population in lower excited states in both cases.

Our data constitute important benchmarks for theoretical calculations that are needed in the modelling of stellar photospheres.We compare our experimental findings to different theoretical models and discuss their strengths and shortcomings.

In order to achieve these scientific results, the thesis work involved the development of data preparation and analysis for a frame- and an event-based detector, as well as the development of experimental methods.

We measured the product-state distribution and its dependence on the hydrogen isotope for the mutual neutralization between ¹⁶O⁺ and ^1,2H⁻ at the double electrostatic ion-beam storage ring DESIREE for center-of-mass collision energies below 100 meV. We find at least six product channels into ground-state hydrogen and oxygen in different excited states. The majority of oxygen products populate terms corresponding to 2⁢𝑠²2⁢𝑝³⁢(⁴𝑆^∘)⁢4⁢𝑠 with ⁵S^∘ as the main reaction product. We also observe product channels into terms corresponding to 2⁢𝑠²2⁢𝑝³⁢(⁴𝑆)⁢3⁢𝑝. Collisions with the heavier hydrogen isotope yield a branching into these lower excited states smaller than collisions with ¹H⁻. The observed reaction products agree with the theoretical predictions. The detailed branching fractions, however, differ between the theoretical results, and none of them fully agree with the experiment.

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.

We report on mutual neutralization measurements between 7Li+ and 1H- at effective center-of-mass collision energies in the range of 100 to 350 meV. We find that final states of lithium with principal quantum number n = 3 dominate with 3s separated from the unresolved 3p and 3d states. We measure the 3s branching fraction to be 0.665(12) at 100(16) meV and no significant dependence on collision energy is observed in the studied range. Comparing to previous results on mutual neutralization between 7Li+ and 2H- [G. Eklund et al., Phys. Rev. A 102, 012823 (2020)], we find that 7Li+ collisions with 1H- result in a significantly higher 3s branching fraction than collisions with 2H-. The difference is 0.087(14). The 3s branching fraction of 7Li+ + 1H- and the determined isotope difference are in agreement with results from extended full quantum calculations based on the same input data and numerical method as in Croft et al. [H. Croft, A. S. Dickinson, and F. X. Gadea, J. Phys. B 32, 81 (1999)]. These calculations reveal strong Stueckelberg oscillations of the 3s branching fraction for both isotopes.

We studied the mutual neutralization of Li⁺ and H^- at effective collision energies of a few hundred meV, which corresponds to temperatures of around 2000 K, in the double ion storage ring DESIREE.We present a new approach to match beam velocities and a new general analysis method for non-fragmenting mutual neutralization at DESIREE.Our results show two features, which we could clearly assign to the product channel into the electronically   excited  3s state of neutral lithium and an unresolved combination of 3p and 3d final state contributions.Branching fractions into 3s are extracted for ten different collision energies via spectral binning and compared to several theoretical investigations and two previous measurements, which focused on the heavier isotope deuterium.We find a significant isotope effect, as theoretically predicted, but in contrast to previous experimental results. The branching fractions agree well with different theoretical approaches using non-empirical couplings and  best with a combination of ab initio potentials and Landau-Zener transition probabilities.

Time-dependent photodetachment action spectra for the linear hydrocarbon anions C₄H⁻ and C₆H⁻ are investigated using the cryogenic Double ElectroStatic Ion Ring ExpEriment. The radiative cooling characteristics of these ions on the millisecond to seconds timescale are characterized by monitoring changes in their spectra as the ions cool by spontaneous infrared (IR) emission. The average cooling rates, extracted using Non-negative Matrix Factorization, are fit with 1/e lifetimes of 19 ± 2 and 3.0 ± 0.2 s for C₄H⁻ and C₆H⁻, respectively. The cooling rates are successfully reproduced using a simple harmonic cascade model of IR emission. The ultraslow radiative cooling dynamics determined in this work provide important data for understanding the thermal cooling properties of linear hydrocarbon anions and for refining models of the formation and destruction mechanisms of these anions in astrochemical environments.

We report the first experimental evidence of spontaneous electron emission from a homonuclear dimer anion through direct measurements of Ag-2(-) -> Ag-2 + 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.