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.

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.

Negative ions are important in many areas of science and technology, e.g., in interstellar chemistry, for accelerator-based radionuclide dating, and in anti-matter research. They are unique quantum systems where electron-correlation effects govern their properties. Atomic anions are loosely bound systems, which with very few exceptions lack optically allowed transitions. This limits prospects for high-resolution spectroscopy, and related negative-ion detection methods. Here, we present a method to measure negative ion binding energies with an order of magnitude higher precision than what has been possible before. By laser-manipulation of quantum-state populations, we are able to strongly reduce the background from photodetachment of excited states using a cryogenic electrostatic ion-beam storage ring where keV ion beams can circulate for up to hours. The method is applicable to negative ions in general and here we report an electron affinity of 1.461 112 972(87) eV for ¹⁶O.

The mutual neutralisation of O+ with O− has been studied in a double ion-beam storage ring with combined merged-beams, imaging and timing techniques. Branching ratios were measured at the collision energies of 55, 75 and 170 (± 15) meV, and found to be in good agreement with previous single-pass merged-beams experimental results at 7 meV collision energy. Several previously unidentified spectral features were found to correspond to mutual neutralisation channels of the first metastable state of the cation (O+(2Do), τ ≈ 3.6 hours), while no contributions from the second metastable state (O+(2Po), τ ≈ 5 seconds) were observed. Theoretical calculations were performed using the multi-channel Landau–Zener model combined with the anion centered asymptotic method, and gave good agreement with several experimentally observed channels, but could not describe well observed contributions from the O+(2Do) metastable state as well as channels involving the O(3s 5So) state.

We have developed an experimental technique to study charge-and energy-flow processes in sub-eV collisions between oppositely charged, internally cold, ions of atoms, molecules, and clusters. Two ion beams are stored in separate rings of the cryogenic ion-beam storage facility DESIREE, and merged in a common straight section where a set of biased drift tubes is used to control the center-of-mass collision energy locally in fine steps. Here, we present measurements on mutual neutralization between Li+ and D- where a time-sensitive imaging-detector system is used to measure the three-dimensional distance between the neutral Li and D atoms as they reach the detector. This scheme allows for direct measurements of kinetic-energy releases, and here it reveals separate populations of the 3s state and the (3p + 3d) states in neutral Li while the D atom is left in its ground state 1s. The branching fraction of the 3s final state is measured to be 57.8 +/- 0.7% at a center-of-mass collision energy of 78 +/- 13 meV. The technique paves the way for studies of charge-, energy-, and mass-transfer reactions in single collisions involving molecular and cluster ions in well-defined quantum states.

We present a new high-pressure x-ray photoelectron spectroscopy system dedicated to probing catalytic reactions under realistic conditions at pressures of multiple bars. The instrument builds around the novel concept of a virtual cell in which a gas flow onto the sample surface creates a localized high-pressure pillow. This allows the instrument to be operated with a low pressure of a few millibar in the main chamber, while simultaneously a local pressure exceeding 1 bar can be supplied at the sample surface. Synchrotron based hard x-ray excitation is used to increase the electron mean free path in the gas region between sample and analyzer while grazing incidence <5 degrees close to total external refection conditions enhances surface sensitivity. The aperture separating the high-pressure region from the differential pumping of the electron spectrometer consists of multiple, evenly spaced, micrometer sized holes matching the footprint of the x-ray beam on the sample. The resulting signal is highly dependent on the sample-to-aperture distance because photoemitted electrons are subject to strong scattering in the gas phase. Therefore, high precision control of the sample-to-aperture distance is crucial. A fully integrated manipulator allows for sample movement with step sizes of 10 nm between 0 and -5 mm with very low vibrational amplitude and also for sample heating up to 500 degrees C under reaction conditions. We demonstrate the performance of this novel instrument with bulk 2p spectra of a copper single crystal at He pressures of up to 2.5 bars and C1s spectra measured in gas mixtures of CO + H-2 at pressures of up to 790 mbar. The capability to detect emitted photoelectrons at several bars opens the prospect for studies of catalytic reactions under industrially relevant operando conditions.

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.

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.

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).