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.
When ultracold plasma is generated using the photoionization of laser-cooled atoms, some atoms reach only up to Rydberg states. These, in turn, interact with the free electrons of the plasma and get ionized further, thus enhancing the plasma. Theoretical models until date have used a semiclassical approach that does not explain all the properties of Rydberg ionization. We present an analytical solution for the Rydberg–electron ionization cross section using the Quantum-mechanical scattering process, which shows a good agreement with experimental data. In particular, the dependency of ionization on the Rydberg state is clearly shown in the form of relation with orbital size and the scattering length. This calculation is valid for all alkali atoms and, hence, is useful for estimating the electron density of ultracold plasma.
Abstract Ultracold molecules formed from association of a single Rydberg atom with surrounding atoms or molecules and those from double Rydberg excitations are discussed in this review. Ultralong-range Rydberg molecules possess a novel molecular bond resulting from scattering of the Rydberg electron from the perturber atoms or molecules. The strong interactions between Rydberg atoms in ultracold gases may lead to formation of macroscopic Rydberg macrodimers. The exquisite control over the properties of the Rydberg electron means that interesting and unusual few-body and quantum many-body features can be realized in such systems.
Ultracold molecules formed from association of a single Rydberg atom with surrounding atoms or molecules and those from double Rydberg excitations are discussed in this review. Ultralong-range Rydberg molecules possess a novel molecular bond resulting from scattering of the Rydberg electron from the perturber atoms or molecules. The strong interactions between Rydberg atoms in ultracold gases may lead to formation of macroscopic Rydberg macrodimers. The exquisite control over the properties of the Rydberg electron means that interesting and unusual few-body and quantum many-body features can be realized in such systems.
In the present work very-high-n Rydberg-atoms
(nsim100−nsim400) are used to probe electron-molecule collisions at ultra-low electron energies. Based on the essentially-free-electron model, for sufficiently high n, Rydberg atom-molecule collisions can be described in terms of a binary interaction between the target molecule and the essentially-free Rydberg electron. Since the average kinetic energy of the Rydberg electron is ultra-low
rm(sim85mueV−sim1.4meV), analysis of the very-high-n Rydberg-atom collision data can provide information on electron-molecule scattering at electron energies corresponding to electron temperatures of only $\\sim
1\\sp\\circ$K, which are far below those accessible using any alternate approach.\nRate constants for destruction of very-high-n Rydberg atoms in collisions with various target molecules have been measured. This study focuses on Rydberg electron transfer to an electron-attaching molecule which results in negative ion formation via the reactions
rmK(itnp/)+XYtoKsp++(XY)sp−∗ortoKsp++Xsp−+Yeqno(1)and on rotational energy transfer from polar molecules which leads to Rydberg atom ionization
rmK(itnp/)+XY(itJ/)toKsp++itesp−+XY(itJ/−1)eqno(2)\nThe n dependence of the rate constants for Rydberg-atom destruction depends on the reactions involved. In reaction (1) the rate constant is independent of n whereas in reaction (2) it increases nearly linearly with n. When both reactions are possible, the measured n dependence can be explained in terms of contributions from each process.\nThe essentially-free-electron model suggests that the n dependence of the rate constants for Rydberg-atom destruction reflects the energy dependence of the cross sections of the corresponding free electron-molecule collision processes which are $$\\eqalignno{&e\\sp- + \\rm XY \\to (XY)\\sp{-*}\\ or\\ \\to X\\sp- + Y&(1\\sp\\prime)\\cr &e\\sp- + \\rm XY({\\it J\\/}) \\to {\\it e}\\sp- + XY({\\it J\\/}-1)&(2\\sp\\prime)\\cr}$$Analysis of the data therefore provides the behavior of cross sections for these processes at ultra-low electron energies.