The properties of a Rydberg atom immersed in an ultracold environment were investigated. Two scenarios were considered, one of which involves the neighbouring ground-state atoms arranged in a spatially structured configuration, while the other involves them distributed randomly in space. To calculate the influence of the multiple ground-state atoms on the Rydberg atom, Fermi-pseudopotential was used, which simplified greatly the numerical effort. In many cases, the few-body interaction can be written down analytically which reveals the symmetry properties of the system. In the structured case, we report the first prediction of the formation of ``Rydberg Borromean trimers''. The few-body interactions and the dynamics of the linear A-B-A trimer, where A is the ground-state atom and B is the Rydberg atom, were investigated in the framework of normal mode analysis. This exotic ultralong-range triatomic bound state exists despite that the Rydberg-ground-state interaction is repulsive. Their lifetimes were estimated using both quantum scattering calculations and semi-classical approximations which are found to be typically sub-microseconds. In the disordered case, the Rydberg-excitation spectra of a frozen-gas were simulated, where the nuclear degrees of freedom can be ignored. The systematic change of the spectral shape with respect to the density of the gas and the excitation of the Rydberg atom were found and studied. Some parts of the spectral shape can be described by simple scaling laws with exponents given by the basic properties of the atomic species such as the polarizability and the zero-energy electron-atom scattering length.
The properties of a Rydberg atom immersed in an ultracold environment were investigated. Two scenarios were considered, one of which involves the neighbouring ground-state atoms arranged in a spatially structured configuration, while the other involves them distributed randomly in space. To calculate the influence of the multiple ground-state atoms on the Rydberg atom, Fermi-pseudopotential was used, which simplified greatly the numerical effort. In many cases, the few-body interaction can be written down analytically which reveals the symmetry properties of the system. In the structured case, we report the first prediction of the formation of ``Rydberg Borromean trimers''. The few-body interactions and the dynamics of the linear A-B-A trimer, where A is the ground-state atom and B is the Rydberg atom, were investigated in the framework of normal mode analysis. This exotic ultralong-range triatomic bound state exists despite that the Rydberg-ground-state interaction is repulsive. Their lifetimes were estimated using both quantum scattering calculations and semi-classical approximations which are found to be typically sub-microseconds. In the disordered case, the Rydberg-excitation spectra of a frozen-gas were simulated, where the nuclear degrees of freedom can be ignored. The systematic change of the spectral shape with respect to the density of the gas and the excitation of the Rydberg atom were found and studied. Some parts of the spectral shape can be described by simple scaling laws with exponents given by the basic properties of the atomic species such as the polarizability and the zero-energy electron-atom scattering length.
Combining ultracold atomic gases with the peculiar properties of Rydberg excited atoms gained a lot of theoretical and experimental attention in recent years. Embedded in the ultracold gas, an interaction between the Rydberg atom and the surrounding ground state atoms arises through the scattering of the Rydberg electron from an intruding perturber atom. This peculiar interaction gives rise to a plenitude of previously unobserved effects. Within the framework of the present thesis, this interaction is studied in detail for Rydberg P-states in rubidium. Due to their long lifetime, atoms in Rydberg states are subject to scattering with the surrounding ground state atoms in the ultracold cloud. By measuring their lifetime as a function of the ground state atom flux, we are able to obtain the total inelastic scattering cross section as well as the partial cross section for associative ionisation. The fact that the latter is three orders of magnitude larger than the size of the formed molecular ion indicates the presence of an efficient mass transport mechanism that is mediated by the Rydberg–ground state interaction. The immense acceleration of the collisional process shows a close analogy to a catalytic process. The increase of the scattering cross section renders associative ionisation an important process that has to be considered for experiments in dense ultracold systems. The interaction of the Rydberg atom with a ground state perturber gives rise to a highly oscillatory potential that supports molecular bound states. These so-called ultralong-range Rydberg molecules are studied with high resolution time-of-flight spectroscopy, where we are able to determine the binding energies and lifetimes of the molecular states between the two fine structure split 25P-states. Inside an electric field, we observe a broadening of the molecular lines that indicates the presence of a permanent electric dipole moment, induced by the mixing with high angular momentum states. Due to the mixing of the ground state atom’s hyperfine states by the molecular interaction, we are able to observe a spin-flip of the perturber upon creation of a Rydberg molecule. Furthermore, an incidental near-degeneracy in the underlying level scheme of the 25P-state gives rise to highly entangled states between the Rydberg fine structure state and the perturber’s hyperfine structure. These mechanisms can be used to manipulate the quantum state of a remote particle over distances that exceed by far the typical contact interaction range. Apart from the ultralong-range Rydberg molecules that predominantly consist of only one low angular momentum state, a class of Rydberg molecules is predicted to exist that strongly mixes the high angular momentum states of the degenerate hydrogenic manifolds. These states, the so-called trilobite- and butterfly Rydberg molecules, show very peculiar properties that cannot be observed for conventional molecules. Here we present the first experimental observation of butterfly Rydberg molecules. In addition to an extensive spectroscopy that reveals the binding energy, we are also able to observe the rotational structure of these exotic molecules. The arising pendular states inside an electric field allow us, in comparison to the model of a dipolar rotor, to extract the precise bond length and dipole moment of the molecule. With the information obtained in the present study, it is possible to photoassociate butterfly molecules with a selectable bond length, vibrational state, rotational state, and orientation inside an electric field. By shedding light on various previously unrevealed aspects, the experiments presented in this thesis significantly deepen our knowledge on the Rydberg–ground state interaction and the peculiar effects arising from it. The obtained spectroscopic information on Rydberg molecules and the changed reaction dynamics for molecular ion creation will surely provide valuable data for quantum chemical simulations and provide necessary data to plan future experiments. Beyond that, our study reveals that the hyperfine interaction in Rydberg molecules and the peculiar properties of butterfly states provide very promising new ways to alter the short- and long-range interactions in ultracold many-body systems. In this sense the investigated Rydberg–ground state interaction not only lies right at the interface between quantum chemistry, quantum many-body systems, and Rydberg physics, but also creates many new and fascinating possibilities by combining these fields.
In this work I describe the excitation spectra of Rydberg atoms in ultracold gases of strontium and their decay mechanisms. In a few-body regime, we observe a highly structured spectrum re ecting excitation of ultralong-range molecules consisting of one or more ground-state atoms bound to the Rydberg core in potential wells formed by the Rydbergelectron wave function. In a many-body regime, with hundreds of ground-state atoms within the Rydberg orbital, the Rydberg atoms can be viewed as an impurity in a quantum gas, connecting to important concepts in condensed matter physics. The spectrum for impurity excitation displays signatures of polaronic states, in which the Rydberg atom signi cantly perturbs the density of the background gas. Additionally, decay channels of Rydberg excitations are examined by monitoring the time evolution of Rydberg populations. The measured lifetimes reveal new information on the decay processes of Rydberg molecules and place limits on the time scales over which studies involving Rydberg species in cold, dense atomic gases can be undertaken and limit the coherence times for such measurements.
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.
The work presented in this dissertation represents a comprehensive study on long-range interactions between alkali Rydberg atoms. As a consequence of their size, Rydberg atoms possess very large dipole moments, making them highly sensitive to external fields and to other Rydberg atoms. The strong dipole-dipole interaction between two Rydberg atoms results in a mixing of their angular momentum characters, which is the cornerstone of the work presented here. We describe the ℓ-mixing between various local molecular asymptotes through a residual Coulomb potential, assuming no electron cloud overlap. We then directly diagonalize an interaction Hamiltonian consisting of these Rydberg-Rydberg interactions and spin-orbit (fine structure) coupling in the Hund's case (c). In this manner, we calculate potential energy curves for various molecular symmetries and find that some of these curves exhibit deep potential wells, capable of supporting very extended bound molecular states ( macrodimers). We analyze the specific structure of the ℓ-mixing for these potential wells and derive convenient n-scaling relations for both their equilibrium separations Re and well depths De. We also explore various properties of the macrodimers, including their response to small electric fields and stability with respect to predissociation. We note throughout the dissertation that the detection of such extended dimers could help progress studies in a variety of areas such as exotic, ultracold chemistry and quantum information and computing. To facilitate detection, we propose a scheme to form and study the macrodimers via photoassociation (PA). We present calculated PA lineshapes from two different electronic ground states based on a harmonic trapping model. We find that both PA signals vary significantly with the laser detunings, indicating that different ℓ-characters could be probed at different equilibrium lengths. Finally, we extend the two-body formalism to the case of three interacting Rydberg atoms and present preliminary results for triply excited 58p rubidium atoms along a common axis. We provide a few examples of surface plots corresponding to different local asymptotes, each with a unique three-dimensional "landscape" and discuss the relevance of the physical features. The highlight of our analysis is the appearance of a potential well, which indicates the formation of a linear trimer. ^
Abstract Ultralong-range Rydberg molecules (ULRMs) comprise a Rydberg atom in whose electron cloud are embedded one (or more) ground-state atoms that are weakly-bound through their scattering of the Rydberg electron. The existence of such novel molecular species was first predicted theoretically in 2000 but they were not observed in the laboratory until 2009. Since that time, interest in their chemical properties, physical characteristics, and applications has increased dramatically. We discuss here recent advances in the study of ULRMs. These have yielded a wealth of information regarding low-energy electron scattering in an energy regime difficult to access using alternate techniques, and have provided a valuable probe of non-local spatial correlations in quantum gases elucidating the effects of quantum statistics. Studies in dense environments, where the Rydberg electron cloud can enclose hundreds, or even thousands, of ground-state atoms, have revealed many-body effects such as the creation of Rydberg polarons. The production of overlapping clouds of different cold atoms has enabled the creation of heteronuclear ULRMs. Indeed, the wide variety of atomic and molecular species that can now be cooled promises, through the careful choice of atomic (or molecular) species, to enable the production of ULRMs with properties tailored to meet a variety of different needs and applications.
In this thesis, we investigate few-body physics and many-body physics of ultralong-range Rydberg molecules. Ultralong-range Rydberg molecules are formed through scattering processes between Rydberg electrons and ground state atoms. The huge size of the Rydberg electron's orbit makes the Rydberg electron able to interact with more than one ground state atom in cold atomic gases with atom number densities from 1012 cm−3 to 1014 cm−3. In cold atomic gases, the ground state atoms on average are far away from each other. They are weakly interacting. Depending on the angular momentum state of the Rydberg electron, two types of polyatomic Rydberg molecules have been studied. When the Rydberg electron is in an ns state, the isotropic probability distribution of the Rydberg electron makes the Rydberg electron interact with different ground state atoms equally. The total binding energy is a summation of the binding energy from each scattering process. These additive interactions have been studied using Cs 6s+83s and 6s+90s polyatomic Rydberg molecules in this thesis. When the Rydberg electron is in an l>0 angular momentum state, spatial correlations between different ground state atoms are established through the anisotropic probability distribution of the Rydberg electron. The total binding energy depends on the relative positions of different ground state atoms. These nonadditive interactions are studied using Cs 6s+6s+34d and 6s+6s+36d triatomic Rydberg molecules in this thesis.