The formation of (40)Ca(2)(+) molecular ions is observed in a hybrid (40)Ca magneto-optical and ion trap system. The molecular ion formation process is determined to be photo-associative ionization of ultracold (40)Ca atoms. A lower bound for the two-body rate constant is found to be beta ≥ 2 ± 1 × 10(-15) cm(3) Hz. Ab initio molecular potential curves are calculated for the neutral Ca(2) and ionic Ca(2)(+) molecules and used in a model that identifies the photo-associative ionization pathway. As this technique does not require a separate photo-association laser, it could find use as a simple, robust method for producing ultracold molecular ions.
The formation of (40)Ca(2)(+) molecular ions is observed in a hybrid (40)Ca magneto-optical and ion trap system. The molecular ion formation process is determined to be photo-associative ionization of ultracold (40)Ca atoms. A lower bound for the two-body rate constant is found to be beta ≥ 2 ± 1 × 10(-15) cm(3) Hz. Ab initio molecular potential curves are calculated for the neutral Ca(2) and ionic Ca(2)(+) molecules and used in a model that identifies the photo-associative ionization pathway. As this technique does not require a separate photo-association laser, it could find use as a simple, robust method for producing ultracold molecular ions.
We describe the experimental observation of ultracold NaCs+ molecular formation in a novel two-species magneto-optical trap. We interpret our observations in terms of a photoassociative ionization pathway similar to that observed in a sodium trap: $\mathrm{Na}+\mathrm{Cs}+\ensuremath{\Elzxh}{\ensuremath{\omega}}_{\mathrm{Na}}+\ensuremath{\Elzxh}{\ensuremath{\omega}}_{\mathrm{Cs}}\ensuremath{\rightarrow}{\mathrm{NaCs}}^{+}{+e}^{\ensuremath{-}}$. We have directly measured the NaCs+ production rate as a function of the excitation laser frequency and intensity elucidating the role of ground-state hyperfine levels. We have observed resonance structures in the frequency-dependent ion rate which we associate with the molecular character of the process.
We present a theoretical analysis of optical pathways for formation of cold ground-state (NaCa)+ molecular ions via an intermediate state. The formation schemes are based on ab initio potential energy curves and transition dipole moments calculated using effective-core-potential methods of quantum chemistry. In the proposed approach, starting from a mixture of cold trapped Ca+ ions immersed into an ultracold gas of Na atoms, (NaCa)+ molecular ions are photoassociated in the excited $E^{1}\mathrm{\ensuremath{\Sigma}}^{+}$ electronic state and allowed to spontaneously decay either to the ground electronic state or an intermediate state from which the population is transferred to the ground state via an additional optical excitation. By analyzing all possible pathways, we find that the efficiency of a two-photon scheme, via either the $B^{1}\mathrm{\ensuremath{\Sigma}}^{+}$ or $C^{1}\mathrm{\ensuremath{\Sigma}}^{+}$ potential, is sufficient to produce significant quantities of ground-state (NaCa)+ molecular ions. A single-step process results in lower formation rates that would require either a high-density sample or a very intense photoassociation laser to be viable.
This dissertation details of the construction of and experiments performed in a hybrid system consisting of a cold neutral atomic magneto-optical trap (MOT) contained within a linear radio-frequency quadrupole ion trap (LQT). The combination of these two workhorses of atomic physics facilitates a variety of developing science such as the controlled investigation of ion-neutral quantum chemistry and the production of ground-state molecular ions. While the primary focus of this work is the production of ultracold molecular ions via sympathetic cooling, there has been investigation of cold (T ~ mK) ion-neutral charge exchange processes in two different ion-neutral pair systems. In addition, a possible method of producing ultracold homonuclear molecular ions via a photo-associative ionization (PAI) pathway is studied in the MOT. The LQT traps ions in spatial overlap with a 40Ca MOT constituting an ultracold buffer gas purposed to sympathetically cool molecular ions.An effective, general method of producing ground-state molecular ions would open a field of physics allowing, for example, precise measurements of molecular transitions which are uniquely sensitive to parity violation, or the possible variation of fundamental constants. Another promising application of cold molecular ions is an implementation of a quantum computing architecture by coupling micro-fabricated strip-line resonators to the microwave rotational transition found in many diatomic molecular ions. The molecular ion BaCl+ is chosen to be used in proof-of-principle sympathetic cooling experiments. Ultimately, a vibrational internal state thermometry experiment shows that the Ca MOT performs very efficiently at quenching the vibrational motion of the BaCl+ molecular ion.As a product of overcoming experimental challenges, this thesis discusses several experiments to characterize trapping and reaction dynamics in the hybrid system. For example, charge transfer measurements are performed with two different laser-cooled atomic ion species, Yb+ and Ba+, which are allowed and disallowed ground-state reaction, respectively. Controlled measurements of these inelastic processes test the cutting edge of quantum theory of ion-neutral interaction in both the ground-state and under optical excitation.
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.
Abstract Experiments with cold ion–atom mixtures have recently opened the way for the production and application of ultracold molecular ions. Here, in a comparative study, we theoretically investigate ground and several excited electronic states and prospects for the formation of molecular ions composed of a calcium ion and an alkali-metal atom: CaAlk+ (Alk = Li, Na, K, Rb, Cs). We use a quantum chemistry approach based on non-empirical pseudopotentials, operatorial core-valence correlation, large Gaussian basis sets, and full configuration interaction method for valence electrons. Adiabatic potential energy curves, spectroscopic constants, and transition and permanent electric dipole moments are determined and analyzed for the ground and excited electronic states. We examine the prospects for ion-neutral reactive processes and the production of molecular ions via spontaneous radiative association and laser-induced photoassociation. After that, spontaneous and stimulated blackbody radiation transition rates are calculated and used to obtain radiative lifetimes of vibrational states of the ground and first-excited electronic states. The present results pave the way for the formation and spectroscopy of calcium–alkali-metal-atom molecular ions in modern experiments with cold ion–atom mixtures.
A dual hybrid ion–neutral trap has been built to study collisions between a cloud of ultracold atoms and small numbers of co-trapped atomic or molecular ions, in a common volume. Ultracold Na atoms are trapped in a vapour-cell magneto-optical trap (MOT), via a single-mode frequency-stabilized ring-dye laser, with repumping. A linear rf quadrupole Paul ion trap, centred on the MOT, co-traps selected atomic or molecular ions, for example Ca+. Control of the initial ion temperature involves laser cooling Ca+ ions via the resonant Fraunhofer K line at 397 nm. We showed the rf ion trap can operate simultaneously with the MOT without destroying the ultracold atom cloud. The goal is to investigate the physics of ion–neutral sympathetic cooling, the cooling by neutrals of translationally cold and vibrorotationally hot molecular ions (e.g. Na2 +(v*, J*)), and the observation of other ion–neutral processes near 0 K, of potential interest in astrophysics.