J. Mikosch

Imaging nucleophilic substitution dynamics.

Anion-molecule nucleophilic substitution (SN2) reactions are known for their rich reaction dynamics, caused by a complex potential energy surface with a submerged barrier and by weak coupling of the relevant rotational-vibrational quantum states. The dynamics of the SN2 reaction of Cl– + CH3I were uncovered in detail by using crossed molecular beam imaging. As a function of the collision energy, the transition from a complex-mediated reaction mechanism to direct backward scattering of the I– product was observed experimentally. Chemical dynamics calculations were performed that explain the observed energy transfer and reveal an indirect roundabout reaction mechanism involving CH3 rotation.

Action spectroscopy and temperature diagnostics of H3+ by chemical probing

Infrared absorption spectroscopy of few hundred H+(3) ions trapped in a 22-pole ion trap is presented using chemical probing as a sensitive detection technique down to the single ion level. By exciting selected overtone transitions of the (v(1)=0,v(2) (l)=3(1))<--(0,0(0)) vibrational band using an external cavity diode laser an accurate diagnostics measurement of the effective translational and rotational temperatures of the trapped ions was performed. The absolute accuracy of the measured transition frequencies was improved by a factor of four compared to previous plasma spectroscopy measurements using velocity modulation [Ventrudo et al., J. Chem. Phys. 100, 6263 (1994)]. The observed buffer gas cooling conditions in the ion trap indicate how to cool trapped H+(3) ions into the lowest ortho and para rotational states. Future experiments will utilize such an internally cold ion ensemble for state-selected dissociative recombination experiments at the heavy ion storage ring Test Storage Ring (TSR).

Photodetachment of cold OH- in a multipole ion trap.

The absolute photodetachment cross section of OH- anions at a rotational and translational temperature of 170 K is determined by measuring the detachment-induced decay rate of the anions in a multipole radio-frequency ion trap. In comparison with previous results, the obtained cross section shows the importance of the initial rotational-state distribution. Using a tomography scan of the photodetachment laser through the trapped ion cloud, the derived cross section is model-independent and thus features a small systematic uncertainty. The tomography also yields the column density of the OH- anions in the 22-pole ion trap in good agreement with the expected trapping potential of a large field free region bound by steep potential walls.

Velocity map imaging of ion–molecule reactive scattering: The Ar++ N2 charge transfer reaction

We present a velocity map imaging spectrometer for the study of crossed-beam reactive collisions between ions and neutrals at (sub-)electronvolt collision energies. The charge transfer reaction of Ar(+) with N(2) is studied at 0.6, 0.8 and 2.5 eV relative collision energies. Energy and angular distributions are measured for the reaction product N. The differential cross section, as analyzed with a Monte Carlo reconstruction algorithm, shows significant large angle scattering for lower collision energies in qualitative agreement with previous experiments. Significant vibrational excitation of N(+)(2) is also observed. This theoretically still unexplained feature indicates the presence of a low energy scattering resonance.

Planar multipole ion trap

We report on the realization of a chip-based multipole ion trap manufactured using microelectromechanical systems technology, requiring minimal manual alignment of the electrodes. It provides ion confinement in an almost field-free volume between two planes of radiofrequency electrodes, deposited on glass substrates, which allows for optical access to the trap. An analytical model of the effective trapping potential is presented and compared with numerical calculations. Stable trapping of argon ions is achieved, and a lifetime of 16 s is measured. Electrostatic charging of the chip surfaces is studied and found to agree with a numerical estimate.

Evaporation of buffer gas-thermalized anions out of a multipole rf ion trap

We identify plain evaporation of ions as the fundamental loss mechanism out of a multipole ion trap. Using thermalized negative Cl- ions we find that the evaporative loss rate is proportional to a Boltzmann factor. This thermodynamic description allows us to extract the effective depth of the ion trap. As a function of the rf amplitude we find two distinct regimes related to the stability of motion of the trapped ions. For low amplitudes the entire trap allows for stable motion and the trap depth increases with the rf field. For larger rf amplitudes rapid energy transfer from the field to the ion motion can occur at large trap radii, which leads to a reduction of the effective trapping volume. In this regime the trap depth decreases again with increasing rf amplitude. We give an analytical parametrization of the trap depth for various multipole traps that allows predictions of the most favorable trapping conditions.

How can a 22-pole ion trap exhibit ten local minima in the effective potential?

The column density distribution of trapped OH− ions in a 22-pole ion trap is measured for different trap parameters. The density is obtained from position-dependent photodetachment rate measurements. Overall, agreement is found with the effective potential of an ideal 22-pole. However, in addition, we observe ten distinct minima in the trapping potential, which indicate a breaking of the 22-fold symmetry. Numerical simulations show that a displacement of a subset of the radiofrequency electrodes can serve as an explanation for this symmetry breaking.

Electron collisions and rovibrational action spectroscopy of cold H3+ molecules

Electron recombination of H3+ has found a lot of attention due to its outstanding relevance for the chemistry of the interstellar medium (ISM) and its role as a benchmark for the treatment of dissociative recombination (DR) of polyatomic ions. We report DR measurements performed at the TSR storage ring utilizing a cryogenic ion trap injector. Furthermore, a chemical probing spectroscopy technique is described that allows for a very sensitive monitoring of the populated states inside the ion injector. Since H3+ exists in two different nuclear spin modifications, a controlled manipulation of the ortho/para fraction is needed in order to perform state-selective measurements.

Kinematically complete reaction dynamics of slow ions

An experiment for crossed beam imaging has been developed for kinematically complete studies of the reaction dynamics of ion-molecule collisions. Here we report on this technique and on recent results regarding the charge transfer reaction of Ar+ + N2. We speculate that the experimental observation of N2+ product ions with unexpectedly high vibrational excitation may be caused by a Feshbach scattering resonance and propose further theoretical work on this reaction. Furthermore we discuss how future collision experiments of molecular ions and clusters will utilize a radiofrequency 22pole trap for internal cooling of the ions prior to the interaction.

Towards state selective measurements of the H3+ dissociative recombination rate coefficient

Ion storage and trapping techniques in connection with efficient internal state control and diagnostic for molecular ions offer the potential of providing rate coefficients for the dissociative recombination of H3+ for well-defined initial rotational states, required for understanding the role of this ion in the interstellar medium and other cold environments. Information on the vibrational and rotational excitation in stored H3+ ion beams, as obtained from experiments at the ion storage ring TSR, is reviewed. In addition, the arrangement of the TSR injector trap, using buffer gas cooling in a cryogenic radiofrequency multipole structure to inject pulses of internally cold H3+ ions into the TSR via a high-energy accelerator, is outlined. An account is given of tests towards the in-situ diagnostic of rotational level populations, where laser transitions between low-lying rovibrational levels could be detected in dilute H3+ ion ensembles using chemical probing in the radiofrequency multipole ion trap.