We show that the dipole-dipole interaction between two Rydberg atoms can give rise to long-range molecules. The binding potential arises from two states that converge to different separated-atom asymptotes. These states interact weakly at large distances, but start to repel each other strongly as the van der Waals interaction turns into a resonant dipole-dipole interaction with decreasing separation between the atoms. This mechanism leads to the formation of an attractive well for one of the potentials. If the two separated-atom asymptotes come from the small Stark splitting of an atomic Rydberg level, which lifts the Zeeman degeneracy, the depth of the well and the location of its minimum are controlled by the external electric field. We discuss two different geometries that result in a localized and a donut-shaped potential, respectively.
We show that the dipole-dipole interaction between two Rydberg atoms can give rise to long-range molecules. The binding potential arises from two states that converge to different separated-atom asymptotes. These states interact weakly at large distances, but start to repel each other strongly as the van der Waals interaction turns into a resonant dipole-dipole interaction with decreasing separation between the atoms. This mechanism leads to the formation of an attractive well for one of the potentials. If the two separated-atom asymptotes come from the small Stark splitting of an atomic Rydberg level, which lifts the Zeeman degeneracy, the depth of the well and the location of its minimum are controlled by the external electric field. We discuss two different geometries that result in a localized and a donut-shaped potential, respectively.
We show that the resonant dipole-dipole interaction can give rise to bound states between two and three Rydberg atoms with nonoverlapping electron clouds. The dimer and trimer states arise from avoided level crossings between states converging to different fine-structure manifolds in the limit of separated atoms. We analyze the angular dependence of the potential wells, characterize the quantum dynamics in these potentials, and discuss methods for their production and detection. Typical distances between the atoms are of the order of several micrometers which can be resolved in state-of-the-art experiments. The potential depths and typical oscillation frequencies are about one order of magnitude larger as compared to the dimer and trimer states investigated by M. Kiffner et al. [Phys. Rev. A 86, 031401(R) (2012)] and M. Kiffner, W. Li, and D. Jaksch [Phys. Rev. Lett. 111, 233003 (2013)], respectively. We find that the dimer and trimer molecules can be aligned with respect to the axis of a weak electric field.
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. ^
We present a novel binding mechanism where a neutral Rydberg atom and an atomic ion form a molecular bound state at a large internuclear distance. The binding mechanism is based on Stark shifts and level crossings that are induced in the Rydberg atom due to the electric field of the ion. At particular internuclear distances between the Rydberg atom and the ion, potential wells occur that can hold atom–ion molecular bound states. Apart from the binding mechanism, we describe important properties of the long-range atom–ion Rydberg molecule, such as its lifetime and decay paths, its vibrational and rotational structure, and its large dipole moment. Furthermore, we discuss methods of how to produce and detect it. The unusual properties of the long-range atom–ion Rydberg molecule give rise to interesting prospects for studies of wave packet dynamics in engineered potential energy landscapes.
Ultra-cold long-range Rydberg-ground molecule consisting of a Rydberg atom and one or more ground-state atoms is formed by low-energy scattering between the Rydberg electron and ground-state atoms located inside the Rydberg electron’s wave function. The low-energy scattering interaction, initially investigated by Fermi and Omont, has been predicted to lead to molecular binding in a novel type of Rydberg molecules, including the trilobite and butterfly molecules. Their unconventional binding mechanism, which is unlike covalent, or ionic, or van der Waals bonds, results in loosely bound molecules with bond lengths on the order of thousands of Bohr radius. This kind of molecule with large size and huge permanent electric dipole moment is a good candidate for realizing the certain strongly correlated many-body gases and for quantum information processing, as well as for dipolar quantum gases and spin systems with long-range interactions. Consequently, these molecules have received considerable attention in recent years. In this paper, we review the recent theoretical and experimental investigations of ultra-cold long-range Rydberg-ground molecules, including the scattering interaction between the Rydberg electron and ground-state atom and the resulting adiabatic potential curves, experimental observations of photo-associated Rydberg-ground molecules spectra, as well as the measurements of permanent electric dipole moment. Ultra-cold long-range Rydberg-ground molecules are prepared by photoassociation in a high-density cold atom sample. Therefore, the Rydberg electron can bind several ground-state atoms to form a polyatomic Rydberg-ground molecule. The permanent molecular electric-dipole moments are revealed by spectral line broadening in the electric fields. The latest research pointed out that the permanent electric dipole moments of the Cs nDJ -type Rydberg-ground molecules are negative, which is different from the previous reports (the electric dipole moments are positive). The negative sign reflects a deficiency of Rydberg-electron density near the ground-state perturber, which is caused by electronic configuration mixing.
Rydberg molecule, formed by one or more Rydberg atoms, exhibits remarkable properties, including an exceptionally large spatial extent, rich rovibrational level structures, permanent electric dipole moments, and a pronounced sensitivity to external fields. Based on the underlying binding mechanisms, Rydberg molecules can be divided into three categories, the ground-Rydberg molecule that is bound via a low-energy electron-atom scattering interaction between ground atom and Rydberg electron, the Rydberg-Rydberg molecule that is bound via a long-range electrostatic interaction between Rydberg atoms, and the ion-Rydberg molecule that is bound via single- or multi-polar interactions between Rydberg atom and ion. This review focuses on recent theoretical and experimental advances in diatomic Rydberg molecules, covering their formation and binding mechanisms, potential energy curves, experimental observations, and spectroscopic properties, with the aim of providing a comprehensive overview of the current state and future prospects of this rapidly developing field.
Few-body interactions offer the opportunity to study the isolated atom to few-body coupled molecules, and to condensed matter transitions. Atoms in molecules and in condensed matters are coupled by different orders of multipole–multipole interactions, which all stem from different orders of approximations from coulomb interactions between multiple charges. The lowest order multipole–multipole interaction is the dipole–dipole interaction, which is proportional to the size of the dipole. In this article, we use Rydberg atoms, which have more than 1000 times greater electric dipoles than the ground state atoms, to study the van der Waals interaction between few bodies. In addition to the large dipoles, the kinetic energy of the atoms is significantly reduced by reducing the temperature, which makes these interactions stable and observable. Here, we report on the 2D and 3D few-body interaction potentials and possible ways of creating semistable molecules in such an ultracold Rydberg gas with a temperature of ≈100 nK. Although we use Rydberg atoms in this article, this calculation can be applied to other states too. The results reported here are useful for studying repulsive van der Waals interactions and creating ultracold molecules.