Hybridization of Rydberg Electron Orbitals by Molecule Formation.

The formation of ultralong-range Rydberg molecules is a result of the attractive interaction between a Rydberg electron and a polarizable ground-state atom in an ultracold gas. In the nondegenerate case, the backaction of the polarizable atom on the electronic orbital is minimal. Here we demonstrate how controlled degeneracy of the respective electronic orbitals maximizes this backaction and leads to stronger binding energies and lower symmetry of the bound dimers. Consequently, the Rydberg orbitals hybridize due to the molecular bond.

From molecular spectra to a density shift in dense Rydberg gases.

In Rydberg atoms, at least one electron is excited to a state with a high principal quantum number. In an ultracold environment, this low-energy electron can scatter off a ground state atom allowing for the formation of a Rydberg molecule consisting of one Rydberg atom and several ground state atoms. Here we investigate those Rydberg molecules created by photoassociation for the spherically symmetric S-states. A step by step increase of the principal quantum number up to n=111 enables us to go beyond the previously observed dimer and trimer states up to a molecule, where four ground state atoms are bound by one Rydberg atom. The increase of bound atoms and the decreasing binding potential per atom with principal quantum number results finally in an overlap of spectral lines. The associated density-dependent line broadening sets a fundamental limit, for example, for the optical thickness per blockade volume in Rydberg quantum optics experiments.

Alignment of D-state Rydberg molecules.

We report on the formation of ultralong-range Rydberg D-state molecules via photoassociation in an ultracold cloud of rubidium atoms. By applying a magnetic offset field on the order of 10 G and high resolution spectroscopy, we are able to resolve individual rovibrational molecular states. A full theory, using a Fermi pseudopotential approach including s- and p-wave scattering terms, reproduces the measured binding energies. The calculated molecular wave functions show that in the experiment we can selectively excite stationary molecular states with an extraordinary degree of alignment or antialignment with respect to the magnetic field axis.