Rydberg atoms have an electron in a state with a very high principal quantum number, and as a result can exhibit unusually long-range interactions. One example is the bonding of two such atoms by multipole forces to form Rydberg-Rydberg molecules with very large internuclear distances. Notably, bonding interactions can also arise from the low-energy scattering of a Rydberg electron with negative scattering length from a ground-state atom. In this case, the scattering-induced attractive interaction binds the ground-state atom to the Rydberg atom at a well-localized position within the Rydberg electron wavefunction and thereby yields giant molecules that can have internuclear separations of several thousand Bohr radii. Here we report the spectroscopic characterization of such exotic molecular states formed by rubidium Rydberg atoms that are in the spherically symmetric s state and have principal quantum numbers, n, between 34 and 40. We find that the spectra of the vibrational ground state and of the first excited state of the Rydberg molecule, the rubidium dimer Rb(5s)-Rb(ns), agree well with simple model predictions. The data allow us to extract the s-wave scattering length for scattering between the Rydberg electron and the ground-state atom, Rb(5s), in the low-energy regime (kinetic energy, <100 meV), and to determine the lifetimes and the polarizabilities of the Rydberg molecules. Given our successful characterization of s-wave bound Rydberg states, we anticipate that p-wave bound states, trimer states and bound states involving a Rydberg electron with large angular momentum-so-called trilobite molecules-will also be realized and directly probed in the near future.

We report on strong van der Waals blockade in two-photon Rydberg excitation of ultracold magnetically trapped 87Rb atoms. The excitation dynamics was investigated for a large range of densities and laser intensities and shows a full saturation and a strong suppression with respect to single-atom behavior. The observed scaling of the initial increase with density and laser intensity provides evidence for coherent collective excitation. This coherent collective behavior, that was observed for up to several thousand atoms per blockade volume, is generic for all mesoscopic systems which are able to carry only one single quantum of excitation.

In a combined experimental and theoretical effort we report on two novel types of ultracold long-range Rydberg molecules. First, we demonstrate the creation of triatomic molecules of one Rydberg atom and two ground-state atoms in a single-step photoassociation. Second, we assign a series of excited dimer states that are bound by a so far unexplored mechanism based on internal quantum reflection at a steep potential drop. The properties of the Rydberg molecules identified in this work qualify them as prototypes for a new type of chemistry at ultracold temperatures.

Permanent electric dipole moments in molecules require a breaking of parity symmetry. Conventionally, this symmetry breaking relies on the presence of heteronuclear constituents. We report the observation of a permanent electric dipole moment in a homonuclear molecule in which the binding is based on asymmetric electronic excitation between the atoms. These exotic molecules consist of a ground-state rubidium (Rb) atom bound inside a second Rb atom electronically excited to a high-lying Rydberg state. Detailed calculations predict appreciable dipole moments on the order of 1 Debye, in excellent agreement with the observations.

Rydberg atoms provide a wide range of possibilities to tailor interactions in a quantum gas. Here, we report on Rydberg excitation of Bose-Einstein condensed 87Rb atoms. The Rydberg fraction was investigated for various excitation times and temperatures above and below the condensation temperature. The excitation is locally blocked by the van der Waals interaction between Rydberg atoms to a density-dependent limit. Therefore, the abrupt change of the thermal atomic density distribution to the characteristic bimodal distribution upon condensation could be observed in the Rydberg fraction. The observed features are reproduced by a simulation based on local collective Rydberg excitations.