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.

We perform a comparative analysis of different computational approaches employed to explore the electronic structure of ultralong-range Rydberg molecules. Employing the Fermi pseudopotential approach, where the interaction is approximated by an s-wave bare delta function potential, one encounters a non-convergent behavior in basis set diagonalization. Nevertheless, the energy shifts within the first order perturbation theory coincide with those obtained by an alternative approach relying on Green's function calculation with the quantum defect theory. A pseudopotential that yields exactly the results obtained with the quantum defect theory, i.e. beyond first order perturbation theory, is the regularized delta function potential. The origin of the discrepancies between the different approaches is analytically explained.

We investigate the impact of an electric field on the structure of ultralong-range polar diatomic Rubidium Rydberg molecules. Both the s-wave and p-wave interactions of the Rydberg electron and the neutral ground state atom are taken into account. In the presence of the electric field the angular degree of freedom between the electric field and the internuclear axis acquires vibrational character and we encounter two-dimensional oscillatory adiabatic potential energy surfaces with an antiparallel equilibrium configuration. The electric field allows to shift the corresponding potential wells in such a manner that the importance of the p-wave interaction can be controlled and the individual wells are energetically lowered at different rates. As a consequence the equilibrium configuration and corresponding energetically lowest well move to larger internuclear distances for increasing field strength. For strong fields the admixture of non-polar molecular Rydberg states leads to the possibility of exciting the large angular momentum polar states via two-photon processes from the ground state of the atom. The resulting properties of the electric dipole moment and the vibrational spectra are analyzed with varying field strength.

We investigate polyatomic ultralong-range Rydberg molecules consisting of three ground state atoms bound to a Rydberg atom via s-and p-wave interactions. By employing the finite basis set representation of the unperturbed Rydberg electron Green's function we reduce the computational effort to solve the electronic problem substantially. This method is subsequently applied to determine the potential energy surfaces of triatomic systems in electronic s-and p-Rydberg states.Their molecular geometry and resulting vibrational structure are analyzed within an adiabatic approach that separates the vibrational bending and stretching dynamics. This procedure yields information on the radial and angular arrangement of the nuclei and indicates in particular that kinetic couplings between bending and stretching modes induce a linear structure in triatomic l = 0 ultralong-range Rydberg molecules.

We show the existence of ultra-long-range giant dipole molecules formed by a neutral alkali ground state atom that is bound to the decentered electronic wave function of a giant dipole atom. The adiabatic potential surfaces emerging from the interaction of the ground state atom with the giant dipole electron posses a rich topology depending on the degree of electronic excitation. Binding energies and the vibrational motion in the energetically lowest surfaces are analyzed by means of perturbation theory and exact diagonalization techniques. The resulting molecules are truly giant with internuclear distances up to several µm. Finally, we demonstrate the existence of intersection manifolds of excited electronic states that potentially lead to a vibrational decay of the ground state atom dynamics.