In this thesis we have studied the stability of ions that are stored in isolation using different laser probing techniques. Laser photodetachment threshold spectroscopy (LPTS) was used for high-precision measurements of electron affinities, an inherent property of atomic and molecular systems important for fundamental research and numerous applications, e.g., for antimatter research or accelerator-based nuclear dating. The measured electron affinities in this thesis include atomic cesium ¹³³Cs and oxygen ¹⁶O, and two fullerenes molecules, C₆₀ and C₇₀. In addition, we have studied the cooling dynamics of ions, relevant to astrophysics, in new time domains and in unprecedented detail. Here, we implement action spectroscopy techniques in DESIREE, a cryogenically cooled electrostatic ion-storage ring with outstanding vacuum conditions. The studied molecules include polycyclic aromatic hydrocarbons (C₁₀H₇CN⁺, C₁₈H₁₂⁺), carbon chains (C₄H⁻, C₆H⁻) and fullerenes (C₆₀⁻ and C₇₀⁻ ). These cooling dynamic experiments were aided by ab initio calculations and numerical simulations in order to unveil the importance of the different relaxation mechanisms that internally excited ions undergo, which determine their survival probabilities. The results presented in this thesis may play an important role for astrophysical modelling, which aims to deepen the understanding of the evolution of molecules in outer space.

An electrospray ion source has been coupled to a cryogenic electrostatic ion-beam storage ring to enable experimental studies of the fundamental properties of biomolecular ions and their reactions in the gas phase on longer timescales than with previous instruments. Using this equipment, we have measured the vibrational radiative cooling rate of the deprotonated anion of the chromophore of the cyan fluorescent protein, a color-shifted mutant of the iconic green fluorescent protein. Time-resolved dissociation rates of collisionally activated ions are first measured to benchmark a model of the dissociation rate coefficient. Storage time-dependent laser-induced dissociation rates are then measured to probe the evolution of the internal energy distribution of the stored ion ensemble. We find that significant heating of the electrosprayed ions occurs upon their extraction from the ion source, and that the radiative cooling rate is consistent with the prediction of a simple harmonic cascade model of vibrational relaxation.

Negative ions are unique quantum systems where electron correlation plays a decisive role in determining their properties. The lack of optically allowed transitions prevents traditional optical spectroscopy and the electron affinity is, therefore, for most elements, the only atomic quantity that can be determined with high accuracy. In this work, we present a high-precision experimental determination of the electron affinity of cesium. A collinear laser-ion beam apparatus was used to investigate the partial photodetachment cross section for the cesium anion, leaving the neutral atom in the 6p 2P3/2 excited state. A resonance ionization scheme was used to obtain final-state selectivity, which enabled the investigation of a sharp onset of the cross section associated with a Wigner s-wave threshold behavior. The electron affinity was determined to be 0.471 598 3(38) eV.

We have studied the stability of C₅₉ anions as a function of time, from their formation on femtosecond timescales to their stabilization on second timescales and beyond, using a combination of theory and experiments. The C^-₅₉ fragments were produced in collisions between C₆₀ fullerene anions and neutral helium gas at a velocity of 90 km s⁻¹ (corresponding to a collision energy of 166 eV in the center-of-mass frame). The fragments were then stored in a cryogenic ion beam storage ring at the DESIREE facility, where they were followed for up to 1 minute. Classical molecular dynamics simulations were used to determine the reaction cross section and the excitation energy distributions of the products formed in these collisions. We find that about 15% of the C^-₅₉ ions initially stored in the ring are intact after about 100 ms and that this population then remains intact indefinitely. This means that C₆₀ fullerenes exposed to energetic atoms and ions, such as stellar winds and shock waves, will produce stable, highly reactive products, like C₅₉, that are fed into interstellar chemical reaction networks.

Negative ions, which are formed when an electron is attached to a neutral system, are unique quantum systems. The lack of a long-range Coulomb force causes the inter-electronic interactions to become relatively more important. As a consequence, the independent particle model, which adequately describes atomic structure under normal conditions, breaks down. The alkali negative ions, with a closed valence s-shell, are among the simplest anionic systems. Hence, they can favorably be used to benchmark atomic theory. In this work, we have determined the electron affinity of 85Rb by measuring the relative partial photodetachment cross section of the negative ion, leaving the residual atom in the 5p 2 P 3 / 2 excited state. Resonance ionization spectroscopy allows for state selectivity and the ability to measure the Wigner s-wave threshold onset of the photodetachment process. The electron affinity of 85Rb was determined to be 485.887(6) meV.

Polycyclic aromatic hydrocarbons have widely been conjectured to be ubiquitous in space, as supported by the recent discovery of two isomers of cyanonaphthalene, indene, and 2-cyanoindene in the Taurus molecular cloud-1 using radioastronomy. Here, the photoionization dynamics of 1-cyanonaphthalene (1-CNN) are investigated using synchrotron radiation over the hν = 9.0–19.5 eV range, revealing that prompt autoionization from the plasmon resonance dominates the photophysics for hν = 11.5–16.0 eV. Minimal photo-induced dissociation, whether originating from an excited state impulsive bond rupture or through internal conversion followed by a statistical bond cleavage process, occurs over the microsecond timescale (as limited by the experimental setup). The direct photoionization cross section and photoelectron angular distributions are simulated using an ezDyson model combining Dyson orbitals with Coulomb wave photoejection. When considering these data in conjunction with recent radiative cooling measurements on 1-CNN⁺, which showed that cations formed with up to 5 eV of internal energy efficiently stabilize through recurrent fluorescence, we conclude that the organic backbone of 1-CNN is resilient to photodestruction by VUV and soft XUV radiation. These dynamics may prove to be a common feature for the survival of small polycyclic aromatic hydrocarbons in space, provided that the cations have a suitable electronic structure to support recurrent fluorescence.  

Naphthalene and azulene are isomeric polycyclic aromatic hydrocarbons (PAHs) and are topical in the context of astrochemistry due to the recent discovery of substituted naphthalenes in the Taurus Molecular Cloud-1 (TMC-1). Here, the thermal- and photo-induced isomerization, dissociation, and radiative cooling dynamics of energized (vibrationally hot) naphthalene (Np+) and azulene (Az(+)) radical cations, occurring over the microsecond to seconds timescale, are investigated using a cryogenic electrostatic ion storage ring, affording molecular cloud in a box conditions. Measurement of the cooling dynamics and kinetic energy release distributions for neutrals formed through dissociation, until several seconds after hot ion formation, are consistent with the establishment of a rapid (sub-microsecond) Np+ reversible arrow Az(+) quasi-equilibrium. Consequently, dissociation by C2H2-elimination proceeds predominantly through common Az(+) decomposition pathways. Simulation of the isomerization, dissociation, recurrent fluorescence, and infrared cooling dynamics using a coupled master equation combined with high-level potential energy surface calculations [CCSD(T)/cc-pVTZ], reproduce the trends in the measurements. The data show that radiative cooling via recurrent fluorescence, predominately through the Np+ D-0 <- D-2 transition, efficiently quenches dissociation for vibrational energies up to approximate to 1 eV above dissociation thresholds. Our measurements support the suggestion that small cations, such as naphthalene, may be more abundant in space than previously thought. The strategy presented in this work could be extended to fingerprint the cooling dynamics of other PAH ions for which isomerization is predicted to precede dissociation.

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.

After decades of searching, astronomers have recently identified specific Polycyclic Aromatic Hydrocarbons (PAHs) in space. Remarkably, the observed abundance of cyanonaphthalene (CNN, C10H7CN) in the Taurus Molecular Cloud (TMC-1) is six orders of magnitude higher than expected from astrophysical modeling. Here, we report unimolecular dissociation and radiative cooling rate coefficients of the 1-CNN isomer in its cationic form. These results are based on measurements of the time-dependent neutral product emission rate and kinetic energy release distributions produced from an ensemble of internally excited 1-CNN+ studied in an environment similar to that in interstellar clouds. We find that Recurrent Fluorescence - radiative relaxation via thermally populated electronic excited states - efficiently stabilizes 1-CNN+, owing to a large enhancement of the electronic transition probability by vibronic coupling. Our results help explain the anomalous abundance of CNN in TMC-1 and challenge the widely accepted picture of rapid destruction of small PAHs in space.