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 (similar to 10(-14)) and cryogenic (13 K) operation of DESIREE. The yield of neutral particles from stored beams of Ag-6(-) and Ag-2(-) anions were measured for 100 milliseconds and were found to follow single power-law behavior with millisecond time-scale exponential cutoffs. The Ag-4(-) and Ag-5(-) anions were stored for 60 s 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 determine this behavior. Comparisons with the measurements strongly suggest that the neutral particles detected in these time domains originate from Ag-4(-) -> Ag-3(-) + Ag and Ag-5(-) -> Ag-3(-) +Ag-2 fragmentation processes.
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 use a novel electrostatic ion storage ring to measure the radiative lifetime of the upper level in the 3p 5 P 2 o 1/2 →3p 5 P 2 o 3/2 spontaneous radiative decay in S − 32 to be 503±54 sec . This is by orders of magnitude the longest lifetime ever measured in a negatively charged ion. Cryogenic cooling of the storage ring gives a residual-gas pressure of a few times 10 −14 mbar at 13 K and storage of 10 keV sulfur anions for more than an hour. Our experimental results differ by 1.3σ from the only available theoretical prediction.
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.
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.
In this paper we report the results of a study on the dissociative recombination (DR) of the diacetylene cation, C4D2+, which has been carried out at the ion storage ring CRYRING in Stockholm, Sweden. The energy-dependent absolute DR cross-section as well as the branching fractions at 0 eV collision energy were measured. The DR cross-section was best fitted using the expression σ(E) = (7.5 ± 1.5) × 10−16 × E−(1.29±0.03) cm2 over the collision energy range 1–100 meV. The thermal rate coefficient was deduced from the cross-section to be α(T) = (1.10 ± 0.15) × 10−6 × (T/300)−(0.79±0.03) cm3/s. The reported branching fractions for C4D2+ agree with previous experiments on the DR of C4H2+ performed at the ASTRID storage ring in Aarhus, Denmark, and furthermore, indicate that the DR of C4D2+ possesses only two channels leading to the following products: C4D + D (75%) and C2D + C2D (25%).
We have measured total absolute cross sections for the mutual neutralization (MN) of O- with O+ and 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 multichannel 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.
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 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- or 1.45-eV photons after 46 ms of storage.
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.
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.
Experimental Near-Edge X-ray Absorption Fine-Structure (NEXAFS) spectra of N-methyltrifluoroacetamide (FNMA), which is a peptide model system, measured at the C, N, O and F K-edges are reported. The features in the spectra have been assigned by Static-Exchange (STEX) calculations. Using the same method, we have also assigned previously measured NEXAFS spectra of another peptide model system, N-methylacetamide (NMA). To facilitate the NEXAFS feature assignments, X-ray Photoelectron Spectroscopy (XPS) measurements for NMA and FNMA have been carried out with the aim of obtaining the 1s electron ionization potentials, which are compared with the values predicted by our Hartree-Fock (Delta HF) and Multi Configuration Self Consistent Field (Delta MCSCF) calculations. We also demonstrate an approach to compensate for screening effects that are neglected in the STEX method. Ion yield measurements of FNMA associated with the excitation of several C, N, O, and F K-shell pre-edge resonances have revealed site-specific fragmentation in some cases which we interpret with the aid of our theoretical calculations.
The fragmentation pattern of the peptide model system, N-methylacetamide, is investigated using ion time-of-flight (TOF) spectroscopy after resonant K-shell excitation. Corresponding near-edge X-ray absorption fine structure (NEXAFS) spectra recorded at high resolution at the C1s, N1s and O1s edges are presented. Analysis of the ion TOF data reveals a multitude of fragmentation channels and dissociation pathways. Comparison between the excitation of six different resonances in the vicinity of the C1s, N1s and O1s edges suggests evidence for site-selective bond breaking. In particular the breaking of the peptide bond and the N-C-alpha bond show a clear correlation with resonant excitation at the N1s edge. Also, stronger tendencies towards site-selective bond breaking are found for the generation of single ions compared with ion pairs. Analysis of angular distributions of ions from breakage of the peptide bond yields a fragmentation time of <400 fs.
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 +/- 0.2 K with 94.9 +/- 0.3% of the ions in the rotational ground state. This is consistent with the storage ring temperature of 13.5 +/- 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 +/- 0.1% of approximately one million stored ions are in the J = 0 rotational ground state. We measure the intrinsic lifetime of the J = 1 rotational level to be 145 +/- 28 s.
Radiative cooling of carbon cluster anions C-2n+1(-)(n = 3-5) is investigated using the cryogenic electrostatic ion storage ring DESIREE. Two different strategies are applied to infer infrared emission on slow (milliseconds to seconds) and ultraslow (seconds to minutes) timescales. Initial cooling of the ions over the millisecond timescale is probed indirectly by monitoring the decay in the yield of spontaneous neutralization by thermionic emission. The observed cooling rates are consistent with a statistical model of thermionic electron emission in competition with infrared photon emission due to vibrational de-excitation. Slower cooling over the seconds to minutes timescale associated with infrared emission from low-frequency vibrational modes is probed using time-dependent action spectroscopy. For C(9)(-)and C-11(-), cooling is evidenced by the time-evolution of the yield of photo-induced neutralization following resonant excitation of electronic transitions near the detachment threshold. The cross-section for resonant photo-excitation is at least two orders of magnitude greater than for direct photodetachment. In contrast, C(7)(-)lacks electronic transitions near the detachment threshold.
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).
The determination of the dissociative recombination rate coefficient of H-3(+) has had a turbulent history, but both experiment and theory have recently converged to a common value. Despite this convergence, it has not been clear if there should be a difference between the rate coefficients for ortho-H-3(+) and para-H-3(+). A difference has been predicted theoretically and could conceivably impact the ortho:para ratio of H-3(+) in the diffuse interstellar medium, where H-3(+) has been widely observed. We present the results of an experiment at the CRYRING ion storage ring in which we investigated the dissociative recombination of highly enriched (similar to 83.6%) para-H-3(+) using a supersonic expansion source that produced ions with T-rot similar to 60-100 K. We observed an increase in the low energy recombination rate coefficient of the enriched para-H-3(+) by a factor of similar to 1.25 in comparison to H-3(+) produced from normal H-2 (ortho:para=3:1). The ratio of the rate coefficients of pure para-H-3(+) to that of pure ortho-H-3(+) is inferred to be similar to 2 at low collision energies; the corresponding ratio of the thermal rate coefficients is similar to 1.5 at electron temperatures from 60 to 1000 K. We conclude that this difference is unlikely to have an impact on the interstellar ortho:para ratio of H-3(+).
Dissociative recombination of the deuterated acetaldehyde ion CD3CDO+ has been studied at the heavy-ion storage ring CRYRING, located at the Manne Siegbahn Laboratory, Stockholm, Sweden. Product branching fractions together with absolute DR cross-sections were measured. The branching fractions were determined at a relative collision energy between the ions and the electrons of 0 eV. With a probability of 34% the DR events resulted in no ruptures of bonds between heavy atoms (i.e. no breakage of the C–C bond or the CO bond). In the remaining 66% of the events one of the bonds between the heavy atoms was broken. The energy-dependent cross-section for the DR reaction was measured between 0 and 1 eV relative kinetic energy. In the energy region between 1 meV and 0.2 eV the absolute cross section could be fitted by the expression σ(E) = 6.8 × 10−16E−1.28 cm2, whereas in the energy interval between 0.2 and 1 eV the data were best fitted by σ(E) = 4.1 × 10−16E−1.60 cm2. From these cross section data the thermal rate coefficient (as a function of the electron temperature), α(T) = 9.2 × 10−7 (T/300)−0.72 cm3 s−1 was obtained.
Competing multi-photon ionization processes, some leading to the formation of double core hole states, have been examined in 4-aminophenol. The experiments used the linac coherent light source (LCLS) x-ray free electron laser, in combination with a time-of-flight magnetic bottle electron spectrometer and the correlation analysis method of covariance mapping. The results imply that 4-aminophenol molecules exposed to the focused x-ray pulses of the LCLS sequentially absorb more than two x-ray photons, resulting in the formation of multiple core holes as well as in the sequential removal of photoelectrons and Auger electrons (so-called PAPA sequences).
The fragmentation dynamics in the CH3+H+H channel arising from the dissociative recombination of protonated methane, CH5+, has been investigated with an imaging detector at the CRYRING storage ring. The experimental results imply that this channel proceeds via two-step break-up in which the intermediate CH4 molecule is sufficiently internally excited to further fragment. These observations could go some way to explaining the discrepancy in results reported from ion storage rings and FALP apparatus.
The most up-to-date theoretical calculation on the dissociative recombination (DR) of D2H+ predicts a 2-5 times lower rate coefficient than that obtained experimentally at the Test Storage Ring (TSR). In order to verify the validity either of the experimental results or the theoretical calculations we have studied the DR of D2H+ at the storage ring CRYRING. The rate coefficient has been measured over the interaction energy range from approximate to 0 eV to 50 eV and has been found to have a peak at about 10 eV with a value of 1.6 x 10(-8) cm(3) s(-1), which is in excellent agreement with the result reported from TSR. Taking into account the electron temperature distributions, excellent agreement between the two storage rings measurements is also obtained at smaller interaction energies. The branching fraction analysis has been performed at approximate to 0 eV interaction energy and revealed the following results at the 1 sigma confidence level: N(D+D+H)=76.5%+/-2.2%, N(D-2+H)= 10.0%+/-0.7%, and N(DH+D)=13.5%+/-1.5%. The value of 2N(D-2+H)/N(DH+D)=1.48+/-0.22 implies that formation of D-2 is more favorable than DH.