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Physical Review A

Evaporation of trapped anions studied with a 22-pole ion trap in tandem time-of-flight configuration

Jochen Mikosch, Ulrike Frühling, Sebastian H. Trippel, Rico Otto, P. Hlavenka, D. Schwalm, Matthias Weidemüller, Roland Wester

Published Aug 6, 2008• 39 citations
Publisher

Abstract

We have recently shown [J. Mikosch et al., Phys. Rev. Lett. 98, 223001 (2007)] that the storage time of a thermal ensemble of ions in a multipole radiofrequency (rf) ion trap is ultimately limited by ion evaporation. An analysis of the evaporation rate was used to determine an effective trap depth as a function of the rf amplitude. This revealed that already for moderate rf amplitudes and low average stability parameter $\ensuremath{\eta}$ the loss of ions is driven by nonadiabatic motion of the fastest ions in the rf field. Here we present the details of the experimental procedure together with our experimental apparatus, which combines a 22-pole rf ion trap with tandem time-of-flight mass spectrometry for ion selection and product analysis. We furthermore describe in detail the numerical and analytical models used in the interpretation of our results, which allows one to predict the most favorable trapping conditions in multipole rf ion traps. From a fit to our data we obtain a maximal value of the multipole stability parameter of ${\ensuremath{\eta}}_{\mathit{max}}=0.36\ifmmode\pm\else\textpm\fi{}0.02$ for adiabatic ion motion.

DOI
10.1103/physreva.78.023402

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We have recently shown [J. Mikosch et al., Phys. Rev. Lett. 98, 223001 (2007)] that the storage time of a thermal ensemble of ions in a multipole radiofrequency (rf) ion trap is ultimately limited by ion evaporation. An analysis of the evaporation rate was used to determine an effective trap depth as a function of the rf amplitude. This revealed that already for moderate rf amplitudes and low average stability parameter \ensuremathη\ensuremath{\eta}\ensuremathη the loss of ions is driven by nonadiabatic motion of the fastest ions in the rf field. Here we present the details of the experimental procedure together with our experimental apparatus, which combines a 22-pole rf ion trap with tandem time-of-flight mass spectrometry for ion selection and product analysis. We furthermore describe in detail the numerical and analytical models used in the interpretation of our results, which allows one to predict the most favorable trapping conditions in multipole rf ion traps. From a fit to our data we obtain a maximal value of the multipole stability parameter of \ensuremathηmax=0.36\ifmmode±\else\textpm\fi0.02{\ensuremath{\eta}}_{\mathit{max}}=0.36\ifmmode\pm\else\textpm\fi{}0.02\ensuremathηmax​=0.36\ifmmode±\else\textpm\fi0.02 for adiabatic ion motion.
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.
Abstract. Multipole radiofrequency ion traps are a highly versatile tool to study molecular ions and their interactions in a well-controllable environment. In particular the cryogenic 22-pole ion trap configuration is used to study ion-molecule reactions and complex molecular spectroscopy at temperatures between few Kelvin and room temperatures. This article presents a tutorial on radiofrequency ion trapping in multipole electrode configurations. Stable trapping conditions and buffer gas cooling, as well as important heating mechanisms, are discussed. In addition, selected experimental studies on cation and anion-molecule reactions and on spectroscopy of trapped ions are reviewed. Starting from these studies an outlook on the future of multipole ion trap research is given. Submitted to: J. Phys. B: At. Mol. Phys. Radiofrequency multipole traps 2 1.
Multipole radiofrequency ion traps are a highly versatile tool to study molecular ions and their interactions in a well-controllable environment.In particular the cryogenic 22-pole ion trap configuration is used to study ion-molecule reactions and complex molecular spectroscopy at temperatures between a few kelvin and room temperatures.This paper presents a tutorial on radiofrequency ion trapping in multipole electrode configurations.Stable trapping conditions and buffer gas cooling, as well as important heating mechanisms, are discussed.In addition, selected experimental studies on cation and anion-molecule reactions and on spectroscopy of trapped ions are reviewed.Starting from these studies an outlook on the future of multipole ion trap research is given.
We evaluate the performance of multipole, linear Paul traps for the purpose of studying cold ion–atom collisions. A combination of numerical simulations and analysis based on the virial theorem is used to draw conclusions on the differences that result, by considering the trapping details of several multipole trap types. Starting with an analysis of how a low energy collision takes place between a fully compensated, ultracold trapped ion and an stationary atom, we show that a higher order multipole trap is, in principle, advantageous in terms of collisional heating. The virial analysis of multipole traps then follows, along with the computation of trapped ion trajectories in the quadrupole, hexapole, octopole and do-decapole radio frequency traps. A detailed analysis of the motion of trapped ions as a function of the amplitude, phase and stability of the ion’s motion is used to evaluate the experimental prospects for such traps. The present analysis has the virtue of providing definitive answers for the merits of the various configurations, using first principles.
We present a characterization of the ions’ translational energy distribution in a multipole ion trap. A linear mapping between the energy distribution of the trapped ions onto the ions’ time-of-flight (TOF) to a detector is demonstrated. For low ion temperatures, a deviation from linearity is observed and can be attributed to the emergence of multiple potential minima. The potential landscape of the trapped ions is modeled via the finite element method, also accounting for subtleties such as surface-charge accumulation. We demonstrate the validity of our thermometry method by simulating the energy distribution of the ion ensemble thermalized with buffer gas using a Molecular Dynamics (MD) simulation. A comparison between the energy distribution of trapped ions in different multipole trap configurations—i.e., with hyperbolic rods, cylindrical rods, and cylindrical wires—is provided. With these findings, one can map the temperature of the trapped ions down to the Kelvin regime using their TOF distributions. This enables future studies on sympathetic cooling and chemical reactions involving ions in multipole traps.
We theoretically investigate the dynamics of a trapped ion immersed in a spatially localized buffer gas. For a homogeneous buffer gas, the ion's energy distribution reaches a stable equilibrium only if the mass of the buffer gas atoms is below a critical value. This limitation can be overcome by using multipole traps in combination with a spatially confined buffer gas. Using a generalized model for elastic collisions of the ion with the buffer-gas atoms, the ion's energy distribution is numerically determined for arbitrary buffer-gas distributions and trap parameters. Three regimes characterized by the respective analytic form of the ion's equilibrium energy distribution are found. Final ion temperatures down to the millikelvin regime can be achieved by adiabatically decreasing the spatial extension of the buffer gas and the effective ion trap depth (forced sympathetic cooling).