In this thesis the dynamics of a trapped ion immersed in \na spatially localized buffer gas is investigated. 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 and/or a spatially confined buffer gas. Using a generalized model \nfor 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 \nare found. One of these is a novel regime at large atom-to-ion mass ratios where the final ion temperature can tuned by adiabatically decreasing the spatial extension of the buffer gas and the effective ion trap depth (forced sympathetic cooling). The second part of the thesis presents a hybrid atom ion trap designed for sympathetic cooling of hydroxide anions. In this hybrid trap the anions are immersed in a cloud of laser cooled rubidium atoms. The translational and rovibrational temperatures of the anions is probed by photodetachment tomography and spectroscopy which shows the first ever indication of sympathetic cooling of anions by laser cooled atoms.
In this thesis the dynamics of a trapped ion immersed in \na spatially localized buffer gas is investigated. 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 and/or a spatially confined buffer gas. Using a generalized model \nfor 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 \nare found. One of these is a novel regime at large atom-to-ion mass ratios where the final ion temperature can tuned by adiabatically decreasing the spatial extension of the buffer gas and the effective ion trap depth (forced sympathetic cooling). The second part of the thesis presents a hybrid atom ion trap designed for sympathetic cooling of hydroxide anions. In this hybrid trap the anions are immersed in a cloud of laser cooled rubidium atoms. The translational and rovibrational temperatures of the anions is probed by photodetachment tomography and spectroscopy which shows the first ever indication of sympathetic cooling of anions by laser cooled atoms.
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).
We provide a comprehensive theoretical framework for describing the dynamics of a single trapped ion interacting with a neutral buffer gas, thus extending our previous studies on buffer-gas cooling of ions beyond the critical mass ratio [B. H\"oltkemeier et al., Phys. Rev. Lett. 116, 233003 (2016)]. By transforming the collisional processes into a frame, where the ion's micromotion is assigned to the buffer-gas atoms, our model allows us to investigate the influence of nonhomogeneous buffer-gas configurations as well as higher multipole orders of the radio-frequency trap in great detail. Depending on the neutral-to-ion mass ratio, three regimes of sympathetic cooling are identified which are characterized by the form of the ion's energy distribution in equilibrium. We provide analytic expressions and numerical simulations of the ion's energy distribution, spatial profile, and cooling rates for these different regimes. Based on these findings, a method for actively decreasing the ion's energy by reducing the spatial expansion of the buffer gas arises (forced sympathetic cooling).
This dissertation reports sympathetic cooling of the molecular hydroxyl anion (OH– ) via collisions with ultra cold rubidium (Rb) atoms. The anion’s translational and rotational degrees of freedom were cooled simultaneously. A new generation hybrid atom-ion trap (HAITrap) has been set up, combining an octupole radio frequency (rf) trap for ion storage and a dark-spontaneous force optical trap (darkSPOT) for Rb atoms. While the octupole rf-trap provides a large rf-field-free region decreasing rf-induced collisional heating, the darkSPOT reinforces this effect by locating the atom cloud in the center of the ion trap. The darkSPOT also enables to generate large dark state fractions, suppressing associative detachment and thus ion losses. Evidence on translational sympathetic cooling in the HAITrap was provided using two methods of kinetic thermometry: photodetachment tomography (PD) and measurements of the time of flight (ToF) distribution. The ToF analysis has shown to be more conclusive and numerical simulations validated the experimental findings qualitatively. Based on a one dimensional ToF-temperature mapping, the narrowest measured energy spread would correspond to a temperature of 35 ± 5K. Deviations from thermal distributions were observed, as predicted from a theoretical model developed by our group. Rotational sympathetic cooling was observed via state selective photodetachment (SSPD). This was performed by pre-cooling the atoms with helium buffer gas at 295K and further cooling the ions with Rb at 300 μK. SSPD thermometry yielded a 70% decrease of the anions rotational temperature after interaction with Rb. These experimental findings could have direct applications in cold collision studies, quantum control of chemical reactions or sympathetic cooling of anti-protons.
This Dissertation details the development of state-of-the-art hybrid atom-ion trapping architecture and technique towards increasing the quantum control of matter and the detection of chemical processes at cold temperatures. Experimental work discussed herein is performed primarily using the second-generation of the MOTion trap, a hybrid atom-ion trap consisting of a co-located magneto-optical trap (MOT) and a linear quadrupole trap (LQT), with which 40Ca and a variety of atomic and molecular ions (Yb+, Ba+, BaCl+, and others) can be co-trapped and cooled. Such a device enables the immersion of laser-cooled, ionic Coulomb crystals in diffuse gases of laser-cooled, highly-polarizable neutral atoms, allowing for studies in sympathetic cooling, cold atom-ion chemistry, and nonequilbrium collisional dynamics.In the first of these studies, I discuss our method of sympathetic cooling in which we use a laser-cooled gas of Ca atoms to sympathetically cool BaCl+ ions confined in the LQT. Because of the large polarizability of Ca, this method is found to be extremely efficient at cooling the notoriously difficult vibrational degree of freedom. This technique opens the door to research with general, ultracold, highly-localized molecular ions in the quantum ground-state which are not able to be produced using the more traditional methods of Doppler-cooling or photoassociation.In the study of cold chemistry in the hybrid trap, I characterize a fundamental reaction, known as charge exchange, at the single-particle level in which an electron is transferred from a neutral atom to an atomic ion during an inelastic collision. This low-temperature process is thought to be foundational to the chemistry leading to the formation of stars, planets and interstellar clouds in our universe. Herein I discuss how improved experimental architecture has enabled the determination of reaction rate constants for individual electronic states of the reactants.Our theoretical study of the collisional processes in hybrid atom-ion traps has led to the discovery of surprising nonequilibrium physics which exists in the hybrid trap environment. Herein I outline the collisional dynamics between neutral atoms and atomic ions in the presence of a time-dependent confining potential and describe how these dynamics manifest themselves in the emergence of nonequilbrium phenomena as indicated by bifurcations in steady-state energies of trapped ions. I show how the these dynamics can potentially limit the efficiency and overall viability of using neutral buffer gases to sympathetically cool the translational motion of trapped ions to ultracold temperatures.In addition to these experimental studies, the development of architecture is discussed with focus given to the implementation of a novel time-of-flight mass spectrometer (TOF-MS) for use with hybrid atom-ion traps as well as standard LQTs. This simple, modular device couples radially with the LQT and enables the straightforward mass analysis of trapped species without complications derived from typical experimental difficulties, engineering constraints, and financial concerns. With this robust device we precisely characterize chemical processes which can take place in these hybrid atom-ion traps. Additionally, I describe how this new architecture is used to perform the action spectroscopy of several previously unstudied molecular ions in order to further establish the field of cold molecular ion research and the widespread use of hybrid atom-ion traps.
Sympathetic cooling of trapped ions through collisions with neutral buffer gases is critical to a variety of modern scientific fields, including fundamental chemistry, mass spectrometry, nuclear and particle physics, and atomic and molecular physics. Despite its widespread use over four decades, there remain open questions regarding its fundamental limitations. To probe these limits, here we examine the steady-state evolution of up to 10 barium ions immersed in a gas of three-million laser-cooled calcium atoms. We observe and explain the emergence of nonequilibrium behaviour as evidenced by bifurcations in the ion steady-state temperature, parameterized by ion number. We show that this behaviour leads to the limitations in creating and maintaining translationally cold samples of trapped ions using neutral-gas sympathetic cooling. These results may provide a route to studying non-equilibrium thermodynamics at the atomic level.
This thesis reports on experimental and theoretical studies of the sympathetic cooling of complex molecular ions demonstrating that this general method for cooling atomic and molecular ions is reliable and efficient.
For this purpose, complex molecular ions and barium ions have been confined simultaneously in a linear Paul trap. The complex molecular ions are generated in an electrospray ionization system and transferred to the trap via a 2 m long octopole ion guide. These molecular ions are pre-cooled by room temperature helium buffer gas so that they can be captured by the trap. The atomic barium ions are loaded from a barium evaporator oven and are laser-cooled by a 493 nm cooling laser and a 650 nm repumping
laser. Due to the mutual Coulomb interaction among these charged particles, the kinetic energy of the complex molecular ions can be reduced significantly.
In our experiments we have demonstrated the sympathetic cooling of various molecules (CO2, Alexa Fluor 350, glycyrrhetinic acid, cytochrome c) covering a wide mass range from a few tens to 13000 amu. In every case the molecular ions could be cooled down to millikelvin temperatures.
Photo-chemical reactions of the 138Ba+ ions in the (2P1/2) excited state with gases such as O2, CO2, or N2O, could be observed. If the initial 138Ba+ ion ensemble is cold, the produced 138BaO+ ions are cold as well, with a similar temperature as the laser-cooled barium ions (a few tens of millikelvin). The back-reaction of 138BaO+ ions with neutral CO to 138Ba+ is possible and was observed in our experiments as well.
A powerful molecular dynamics (MD) simulation program has been developed. With this program dynamic properties of ion ensembles, such as sympathetic interactions or heating effects, have been investigated and experimental results have been analyzed to obtain, for example, ion numbers and temperatures. Additionally, the feasibility of nondestructive spectroscopy via an optical dipole excitation and the lineshape of rovibrational
transitions of 1.4 and 5.1 μm have been studied.