This thesis presents simulated and experimental results on ultra-cold Rb Rydberg atoms and ultra-cold Rb2 molecules formed through a photo-association process. Rydbreg results include a study of population dynamics following excitation to a pure Rydberg state as well as interactions with external fields. Photo-association results include an isotopic comparison of molecules created by laser-fields tuned below the 5s+5p asymptote in both stable Rb isotopes 85Rb and 87Rb.
This thesis presents simulated and experimental results on ultra-cold Rb Rydberg atoms and ultra-cold Rb2 molecules formed through a photo-association process. Rydbreg results include a study of population dynamics following excitation to a pure Rydberg state as well as interactions with external fields. Photo-association results include an isotopic comparison of molecules created by laser-fields tuned below the 5s+5p asymptote in both stable Rb isotopes 85Rb and 87Rb.
In this thesis, I report on experiments on the detection and the production of molecules in an ultracold atomic gas. These experiments can be divided into two main parts. The first part is about state-to-state experiments where chemical reaction products are detected in a quantum state resolved way. The second part is about Rydberg molecules. In the first part, I investigate three-body recombination of neutral Rb, which is a chemical reaction leading to the formation of Rb2 dimers. The quantum states of the three-body recombination product molecules are investigated for different initial atomic samples. This includes different atomic hyperfine states and different atomic magnetic sub states that are prepared. The molecular reaction product is state-selectively ionized and detected afterwards. The detection scheme resolves total electron spin, the vibrational, the rotational, the hyperfine and even the magnetic sub state of the product molecules. We determine the population distribution of the product molecules covering the majority of all produced molecules. The insights gained enable us to formulate various propensity rules for the three-body recombination of 87Rb. The second part is furthermore divided into two parts: the investigations of charged and uncharged Rydberg molecules. The investigations of charged Rydberg molecules are the first step towards one of our goals, the photoassociation of BaRb+ or Rb2+ Rydberg molecules. For this work, we have developed a novel method to measure Stark spectra within an ion trap. In experiments with neutral Rb2 Rydberg molecules we observe a complex spin structure of the molecular states. The substructure emerges partially due to a novel, recently predicted spin-orbit interaction of the Rydberg electron and the perturber atom, which we prove for the first time.
This thesis comprises two topics in the field of the ultracold atomic and molecular physics, both involving formation of ultracold 85Rb 2 by photoassociation (PA). Typically, these ground-state molecules are formed mainly in the very highest vibrational levels, rather than the low-v levels that will be required for most future investigations of ultracold molecular physics and chemistry. The first topic of my research is a method for circumventing this problem: resonant enhancement (RE) of photoassociative ground-state molecule production. The key idea of RE is to photoassociate pairs of colliding atoms into an excited state that has a bimodal vibrational probability distribution, with one peak at long range to enhance the photoassociation rate and another at shorter range to enhance radiative decay into deeply bound levels of the ground state. This can be arranged thanks to the strong spin-orbit perturbative interaction between the two 0+u states converging to two different asymptotes, (5s + 5p1/2) and (5s + 5 p3/2). This method enhances ground-state molecule formation in the region well below the dissociation limit. The experimental work described here was done at the University of Connecticut in collaboration with C. P. Koch at the Institut für Theoretische Physik, Freie Universität Berlin, Germany, who performed the theoretical analysis [1].^ The second part of my thesis is the investigation of ultracold molecules in an optical dipole trap. We have constructed a quasi-electrostratic optical trap (QUEST) for 85Rb using a focused CO2 laser [2]. This provides a very high density of ultracold atoms, up to 10 12 cm-3, providing much higher photoassociation rates. It also keeps the molecules trapped once they have formed. The QUEST provides an ample trapping lifetime for both trapped atoms and molecules, yielding about 4-5×106 atoms and about 9×105 high-v molecules. The long lifetime of the trapped molecules and atoms, combined with their high density, allows us to study interactions such as atom-molecule or molecule-molecule collisions in the ultracold regime. A preliminary experiment on Rb2 molecular decay is described. ^
In this dissertation, I explore several aspects of Rydberg physics with laser spectroscopy. The experiments center around the use of a very deep, cavity-generated, one-dimensional optical lattice in a cold atom sample. The optical lattice produces elongated clouds of dense, cold atoms via dipole trapping and is able to generate extreme light shifts in the atoms due to its high intensity. I describe experiments which may be divided into two main classes. In the first, I use the dipole trap to prepare a dense sample of atoms for photoassociation of Rb atom pairs into diatomic Rydberg molecules. The Rydberg molecules are formed by low-energy scattering of the Rydberg electron of one atom from the other atom, which is a ground-state atom. This novel binding mechanism also has relevance for chemical physics. I present binding energy measurements for eight different cases of Rydberg molecules. The binding energies reveal information about electron-atom collisions, such as their scattering lengths, and about the spin couplings present within the molecular system. In the second class of experiments, I introduce two proposed measurements in which the optical lattice is ramped to very high intensity during the laser excitation, creating AC Stark shifts in the transition frequencies. In one measurement, low-lying atomic states are probed. Measurements of the light shifts are expected to yield data on the dynamic polarizability and the photoionization cross section of the 5D3/2-state in rubidium in a 1064-nm light field. I show corresponding preliminary experimental data. The polarizability and photo-ionization cross-section measurements will provide tests of atomic structure theory, which is important both at a fundamental level and for applications such as atomic clocks. In another proposed measurement, Rydberg atoms in the lattice experience ponderomotive shifts and strong mixing of their angular-momentum states, allowing direct optical excitation of the lattice-mixed high-angular-momentum states. I describe the theoretical basis and experimental preparation for spectroscopically characterizing the lattice-mixed states. The ability to optically excite selected high-angular-momentum states without the use of static or RF fields may be useful for quantum information processing and simulation.
Studying ultracold chemical reactions with quantum state resolution reveals details of the reaction processes, especially with single quantum state preparation of the reactants and state-selective detection of reaction products. In this thesis, we investigate two main processes: KRb + KRb → K2 + Rb2 reactions, and Rb and KRb atom-molecule collisions. In the KRb bimolecular reaction, we demonstrate the preservation of quantum coherence in bimolecular reactions for the first time, which is surprising in a reaction considered to be largely chaotic. Additionally, we proposed a coherent control scheme to manipulate product yields across different product channels. These results represent a critical step toward probing quantum coherence and entanglement in the chemical reaction. In atom-molecule collisions between Rb and KRb, we discovered an exceptionally long-lived intermediate complex, KRb2, which can be photo-excited by trapping light. The observed complex lifetime was orders of magnitude longer than theoretical predictions, underscoring the limitations of the current theory. We further explored the dependence of complex lifetimes on the initial quantum states and external electric and magnetic fields, providing additional experimental benchmarks to guide future theoretical work. Separately, we found that inelastic collisions between hyperfine-excited Rb atoms and KRb molecules can lead to rotation excitation of KRb post-collision. By probing the product state distribution, the result suggests that mechanical angular momentum is coupled to the spins. Such couplings are too weak in the current theory models to explain the result. Moreover, our result contradicts state-of-the-art coupled-channel calculations. These suggest that some subtle effects, such as molecular vibration and conical intersections, play a critical role in the reaction dynamics. The final piece of the thesis describes the observation of resonant interaction between a Rydberg atom and an ensemble of polar molecules. Such hybrid quantum systems have been proposed for a wide range of applications. Our work provides an experimental demonstration of resonant dipolar interactions between Rydberg atoms and ultracold polar molecules, paving the way for the realization of hybrid systems for quantum computation and simulation.
In this work the existence of a novel type of molecule is shown whose binding is based solely on electron-atom scattering. These molecules are composed of a Rydberg atom and a ground state atom - here Rb(ns) and Rb(5s) - where the binding arises from scattering of the Rydberg electron from the ground state atom. The ground state atom is bound to the Rydberg wavefunction, which has radii on the order of 100nm, and thus these molecules are of long-range. Although the theoretical description of this interaction goes back to the famous work of Fermi in the year 1934 which was expanded in the following decades by Omont and Greene, the experimental proof of their existence was still missing. Up to now, experimental evidence for the ultralong-range Rydberg molecules was found only in spectral line broadenings. The present experiments have demonstrated the direct photoassociation of these ultralong-range Rydberg molecules for Rb(ns)-Rb(5s) triplet states from a cold and dense sample of rubidium 87 atoms for a range of principal quantum numbers, n, between 34 and 40. The high-resolution photoassociation spectra allowed for the observation of several vibrational states separated by only a few Megahertz. Based on the model by Greene the vibrational ground states v=0 are assigned and the dependence of their binding energy on the principal quantum number, n, is used to extract the triplet s-wave scattering length for electron-Rb(5s) collisions from the data. The remarkably good agreement between experiment and theory for the vibrational ground state v=0 over a range of principal quantum numbers attests to the accuracy of Fermi's original pseudopotential approach in describing interactions in excited multi-atom systems. Aside from this good agreement for the state v=0, the measurements also show that contributions from p-wave scattering cannot be neglected, as a number of excited vibrational states is observed in the experiment that are not predicted from the theory assuming only s-wave scattering. Calculations of Li, Pohl and coworkers have shown that a full solution of the electron-atom scattering is necessary for the assignment of all vibrational states. This work finds the molecular bound states to be very sensitive to both s-wave as well as p-wave electron-atom scattering and the Rydberg molecules turn out to be an accurate experimental platform to study electron-atom collisions in a previously inaccessible ultralow-energy regime. In general, the ultralong-range Rydberg molecules investigated here for rubidium are expected for all species with negative scattering length for electron-atom interaction, e. g. the other alkali atoms. Rydberg atom and ground state atom do not even have to be of the same chemical element, the only requirement is a negative scattering length of the ground state atom for electron scattering. Moreover, the binding force of the Rydberg electron is not restricted to a single ground state atom and molecules with more than one ground state atom can be created. The fact that these exotic molecules have huge bond lengths but nevertheless a vibrational spectrum with several states make a new type of ultracold Rydberg chemistry feasible. In the future, larger polymers or even heteronuclear molecules can be realized, where the number of atoms, the constituent atomic elements and the addressed Rydberg state allow to precisely select the properties of the long-range molecule.
Dipole-dipole interactions, the strongest, longest-range interactions possible between two neutral atoms, cannot be better manifested anywhere else than in a Rydberg atomic system. Rydberg atoms, having high principal quantum numbers n>>1 and dipole moments that scale as n^2, provide a powerful tool to examine dipole-dipole interactions. Therefore, we have studied the production and production rates of strontium Rydberg atoms created using two-photon excitation and have explored their properties in two distinct experiments. In the first experiment, very-high-n (n~300) Rydberg atoms are produced in a tightly collimated atomic beam allowing spectroscopic studies of their energy levels and their Stark effects. Simulations using a two-active-electron model, developed by our theoretical collaborators, allow detailed analysis of the results and are in remarkable agreement with the experimental results. The high density of Rydberg atoms achieved ~ 5*10^5 cm^(-3), in this experiment will allow studies of strongly interacting Rydberg-Rydberg systems. The second experiment, in which a cold strontium Rydberg gas is excited in a magneto-optic trap, features an imaging technique offering both spatial and temporal resolution. We use this technique to observe and study the evolution of an ultra-cold strontium Rydberg gas which reveals the importance of Rydberg-Rydberg interactions in the early stages of this evolution. Strongly interacting Rydberg gas provides an opportunity to realize a very strongly-correlated ultra-cold plasma.