RESUMO
Associative electronic detachment (AED) between anions and neutral atoms leads to the detachment of the anion's electron resulting in the formation of a neutral molecule. It plays a key role in chemical reaction networks, like the interstellar medium, the Earth's ionosphere and biochemical processes. Here, a class of AED involving a closed-shell anion (OH-) and alkali atoms (rubidium) is investigated by precisely controlling the fraction of electronically excited rubidium. Reaction with the ground state atom gives rise to a stable intermediate complex with an electron solely bound via dipolar forces. The stability of the complex is governed by the subtle interplay of diabatic and adiabatic couplings into the autodetachment manifold. The measured rate coefficients are in good agreement with ab initio calculations, revealing pronounced steric effects. For excited state rubidium, however, a lower reaction rate is observed, indicating dynamical stabilization processes suppressing the coupling into the autodetachment region. Our work provides a stringent test of ab initio calculations on anion-neutral collisions and constitutes a generic, conceptual framework for understanding electronic state dependent dynamics in AEDs.
RESUMO
A linear cryogenic 16-pole wire ion trap has been developed and constructed for cryogenic ion spectroscopy at temperatures below 4 K. The trap is temperature-variable, can be operated with different buffer gases, and offers large optical access perpendicular to the ion beam direction. The housing geometry enables temperature measurement during radio frequency operation. The effective trapping potential of the wire-based radio frequency trap is described and compared to conventional multipole ion trap designs. Furthermore, time-of-flight mass spectra of multiple helium tagged protonated glycine ions that are extracted from the trap are presented, which prove very low ion temperatures and suitable conditions for sensitive spectroscopy.
RESUMO
Rotational transitions of the nonlinear triatomic molecular anion NH_{2}^{-} have been observed by terahertz spectroscopy in a cryogenic radio frequency ion trap. Absorption of terahertz photons has been probed by rotational state-dependent photodetachment of the trapped negative ions near the detachment threshold. Using this two-photon scheme, the two lowest rotational transitions for the asymmetric top rotor NH_{2}^{-} have been found. For the para nuclear spin configuration, the 1_{0}â0_{0} transition frequency was determined to be 933 954(2) MHz, and for the ortho configuration the 1_{+1}â1_{-1} transition frequency was determined to be 447 375(3) MHz. This result appears to preclude the recent tentative assignment of an interstellar absorption feature to NH_{2}^{-}.
RESUMO
In the interstellar medium (ISM) ionmolecule 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).