Mutual neutralization reactions play a subtle but crucial role in atmospheric chemistry. The intrinsic gap between typical ionization energies and electron affinities allows cation–anion reactions to produce a broad range of neutral products. Specifically, mutual neutralization of NO⁺ and NO₃^– ions in the presence of water has been proposed to play a key role in the formation of atmospheric nitrous acid (HONO) and, consequently, also OH radical formation. Nevertheless, the mechanisms and products of molecular anion–cation reactions are largely unknown. Here, we present a detailed experimental study of the isolated NO⁺ and NO₃^– reactions, using three-dimensional coincidence imaging of the neutral products of low-energy collisions in merged cation and anion beams. We found that while 15 product channels are energetically accessible, the reaction proceeds exclusively via a single nonadiabatic pathway yielding NO + NO₂ + O. Momentum correlation analysis revealed an intricate nonadiabatic mechanism, initiated by a long-range electron transfer at ∼6 Å distance between the ions, resulting in vibrationally hot NO and an electronically excited NO₃ (²E′) intermediate that undergoes subsequent dissociation, attributed to a conical intersection with the lower lying NO₃ (²E″) state. The mechanistic picture of NO⁺ + NO₃^– neutralization and identification of specific intermediates provides a basis for considering the competing processes that in the presence of water can lead to HONO formation.

We combine cryogenic storage of fullerene anions up to minutes with laser photo-detachment spectroscopy and measure the electron affinities to be 2.684(3) eV for C60 and 2.7665(3) eV for C70, which settle long-standing issues concerning these values. We find that C−70 cools more efficiently than C−60 and that this is due to differences in photon emission from electronically excited states populated by inverse internal conversion (recurrent fluorescence). We also find that intramolecular vibrational redistribution is no longer effective at low internal energies of C−60 or C−70. Radiative cooling becomes extremely slow below intramolecular vibrational redistribution decoupling energies of 0.32(2) and 0.13(3) eV for C−60 and C−70, respectively.

Context. Mutual neutralization (MN) between cations and anions plays an important role in determining the charge balance in certain astrophysical environments. However, empirical data for such reactions involving complex molecular species have been lacking due to challenges in performing experimental studies, leaving the astronomical community to rely on decades-old models with large uncertainties for describing these processes in the interstellar medium.Aims. Our aim is to investigate the MN reaction C60+ + C60− → C60* + C60 for collisions at interstellar-like conditions.Methods. We studied the MN reaction between C60+ and C60− at collision energies of 100 meV using the Double ElectroStatic Ion Ring ExpEriment (DESIREE) and its merged beam capabilities. To aid in the interpretation of the experimental results, semiclassical modeling based on the Landau-Zener approach was performed for the studied reaction.Results. We experimentally identified a narrow range of kinetic energies for the neutral reaction products. Modeling was used to calculate the quantum state-selective reaction probabilities, absolute cross sections, and rate coefficients of these MN reactions, using the experimental results as a benchmark. We compared the MN cross sections with model results for electron attachment to C60 and electron recombination with C60+.Conclusions. Our results show that it is crucial to take mutual polarization effects, the finite sizes, and the final quantum states of both molecular ions into account in order to obtain reliable predictions of MN rates expected to strongly influence the charge balance and chemistry in environments such as dense molecular clouds.

The mutual neutralization of hydronium and hydroxide ions is a fundamental chemical reaction. Yet, there is very limited direct experimental evidence about its intrinsically non-adiabatic mechanism. Chemistry textbooks describe the products of mutual neutralization in bulk water as two water molecules; however, this reaction has been suggested as a possible mechanism for the recently reported spontaneous formation of OH radicals at the surface of water microdroplets. Here, following three-dimensional-imaging of the coincident neutral products of reactions of isolated D3O+ and OD−, we can reveal the non-adiabatic pathways for OD radical formation. Two competing pathways lead to distinct D2O + OD + D and 2OD + D2 product channels, while the proton-transfer mechanism is substantially suppressed due to a kinetic isotope effect. Analysis of the three-body momentum correlations revealed that the D2O + OD + D channel is formed by electron transfer at a short distance of ~4 Å with the formation of the intermediate unstable neutral D3O ground state, while 2OD + D2 products are obtained following electron transfer at a distance of ~10 Å via an excited state of the neutral D3O. (Figure presented.)

Product distributions and dynamics of low-collision-energy mutual neutralisation reactions involving even simple molecular ions are largely unknown. Reactions which involve oxygen ions, e.g., O2+ with O−, are expected to be important in atmospheric phenomena such as sprites and in high-pressure air or oxygen discharges. Here we show, by combining cryogenically stored-and-merged ion beams with coincident product-imaging techniques, that the O2+ with O− mutual neutralisation reaction results predominantly in dissociation of the O2+ molecule. Three competing reaction pathways yields both O(3P) (84%) and O(1D) (16%) products, but no O(1S) products. Analysis of the momentum-correlated dynamics of the reaction reveals the dominance of two-step mechanisms involving the 3pλu and 3sσg Rydberg states of O2. Furthermore, use of the 16,18O2+ isotopologue shows that the reaction products strongly depend on the vibrational levels of the O2+ ion for the channel leading to two O(1D) products.

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.

We have studied the mutual neutralization reaction of vibronically cold NO+ with O- at a collision energy of approximate to 0.1 eV and under single-collision conditions. The reaction is completely dominated by production of three ground-state atomic fragments. We employ product-momentum analysis in the framework of a simple model, which assumes the anion acts only as an electron donor and the product neutral molecule acts as a free rotor, to conclude that the process occurs in a two-step mechanism via an intermediate Rydberg state of NO which subsequently fragments.

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.

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.

Mutual neutralization of hydronium (H₃O⁺) and hydroxide (OH⁻) ions is a very fundamental chemical reaction. Yet, there is only limited experimental evidence about the underlying reaction mechanisms. Here, we report three-dimensional imaging of coincident neutral products of mutual-neutralization reactions at low collision energies of cold and isolated ions in the cryogenic double electrostatic ion-beam storage ring (DESIREE). We identified predominant H2O + OH + H and 2OH + H₂ product channels and attributed them to an electron-transfer mechanism, whereas a minor contribution of H₂O + H₂O with high internal excitation was attributed to proton transfer. The reported mechanism-resolved internal product excitation, as well as collision-energy and initial ion-temperature dependence, provide a benchmark for modeling charge-transfer mechanisms.