Cryogenic 22-pole ion traps have found many applications in ion-molecule reaction kinetics and in high resolution molecular spectroscopy. For most of these applications it is important to know the translational and internal temperatures of the trapped ions. Here, we present detailed rotational state thermometry measurements over an extended temperature range for the two ion/buffer gas systems OH − /He and OD − /HD with ion-to-neutral mass ratios of 4.25 and 6 respectively. The measured rotational temperatures show a termination of the thermalisation with the buffer gas around 25 K, independent of mass ratio and confinement potential of the trap. Different possible explanations for this incomplete thermalisation have been investigated, among them the thermalisation of the buffer gas and the heating due to room temperature blackbody radiation and room temperature gas entering the trap.
In the interstellar medium (ISM) ion–molecule reactions play a key role in forming complex molecules. Since 2006, after the radioastronomical discovery of the first of by now six interstellar anions, interest has grown in understanding the formation and destruction pathways of negative ions in the ISM. Experiments have focused on reactions and photodetachment of the identified negatively charged ions. Hints were found that the reactions of CnH(–) with H2 may proceed with a low (<10(–13) cm(3) s(–1)), but finite rate [Eichelberger, B.; et al. Astrophys. J. 2007, 667, 1283]. Because of the high abundance of molecular hydrogen in the ISM, a precise knowledge of the reaction rate is needed for a better understanding of the low-temperature chemistry in the ISM. A suitable tool to analyze rare reactions is the 22-pole radiofrequency ion trap. Here, we report on reaction rates for Cn(–) and CnH(–) (n = 2, 4, 6) with buffer gas temperatures of H2 at 12 and 300 K. Our experiments show the absence of these reactions with an upper limit to the rate coefficients between 4 × 10(–16) and 5 × 10(–15) cm(3) s(–1), except for the case of C2(–), which does react with a finite rate with H2 at low temperatures. For the cases of C2H(–) and C4H(–), the experimental results were confirmed with quantum chemical calculations. In addition, the possible influence of a residual reactivity on the abundance of C4H(–) and C6H(–) in the ISM were estimated on the basis of a gas-phase chemical model based on the KIDA database. We found that the simulated ion abundances are already unaffected if reaction rate coefficients with H2 were below 10(–14) cm(3) s(–1).
We have studied photodetachment of the amidogen anion as a function of photon energy near the detachment threshold. The detachment spectrum is obtained over the energy range of 6190-6355 cm from the loss rate of the anions from a cryogenic radiofrequency multipole ion trap. By modeling all accessible rotational state-to-state photodetachment transitions, we can assign rotational state-specific thresholds to the measured spectrum. In this way, we have determined the electron affinity of NH to be 6224 ± 1 cm.
We present a method to measure rotational transitions of molecular anions in the terahertz domain by sequential two-photon absorption. Ion excitation by bound-bound terahertz absorption is probed by absorption in the visible on a bound-free transition. The visible frequency is tuned to a state-selective photodetachment transition of the excited anions. This provides a terahertz action spectrum for just few hundred molecular ions. To demonstrate this we measure the two lowest rotational transitions, J =1←0 and J =2←1 of OD − anions in a cryogenic 22-pole trap. We obtain rotational transition frequencies of 598596.08(19) MHz for J =1←0 and 1196791.57(27) MHz for J =2←1 of OD − , in good agreement with their only previous measurement. This two-photon scheme opens up terahertz rovibrational spectroscopy for a range of molecular anions, in particular for polyatomic and cluster anions.
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