We observe long-range $^{85}\mathrm{Rb}$ and $^{87}\mathrm{Rb}$ ($24{D}_{J}+5{S}_{1/2}$) Rydberg molecules for eight different spin couplings, with binding energies up to 440 MHz and subpercent relative uncertainty. Isotopic effects of the molecular binding energies arise from the different masses and nuclear spins. Because the vibrational states involve different spin configurations and cover a wide range of internuclear separations, the states have different dependencies on the $s$-wave and $p$-wave scattering phase shifts for singlet and triplet scattering. Fitting the spectroscopic data, we comprehensively determine all four scattering length functions over the relevant energy range as well as the zero-energy scattering lengths of the two $s$-wave channels. Our unusually high temperature and low density (180 $\ensuremath{\mu}\mathrm{K}$, $1\ifmmode\times\else\texttimes\fi{}{10}^{11}\phantom{\rule{4pt}{0ex}}{\mathrm{cm}}^{\ensuremath{-}3}$) suggest that the molecule excitation occurs through photoassisted collisions.
We observe long-range 85Rb and 87Rb (24DJ+5S1/2) Rydberg molecules for eight different spin couplings, with binding energies up to 440 MHz and subpercent relative uncertainty. Isotopic effects of the molecular binding energies arise from the different masses and nuclear spins. Because the vibrational states involve different spin configurations and cover a wide range of internuclear separations, the states have different dependencies on the s-wave and p-wave scattering phase shifts for singlet and triplet scattering. Fitting the spectroscopic data, we comprehensively determine all four scattering length functions over the relevant energy range as well as the zero-energy scattering lengths of the two s-wave channels. Our unusually high temperature and low density (180 \ensuremathμK, 1\ifmmode×\else\texttimes\fi1011cm\ensuremath−3) suggest that the molecule excitation occurs through photoassisted collisions.
We present high-resolution spectroscopy of Rb2 ultralong-range Rydberg molecules bound by mixed singlet-triplet electron-neutral atom scattering. The mixing of the scattering channels is a consequence of the hyperfine interaction in the ground-state atom, as predicted recently by Anderson et al. [Phys. Rev. A 90, 062518 (2014)]. Our experimental data enable the determination of the effective zero-energy singlet s-wave scattering length for Rb. We show that an external magnetic field can tune the contributions of the singlet and the triplet scattering channels and therefore the binding energies of the observed molecules. This mixing of molecular states via the magnetic field results in observed shifts of the molecular line which differ from the Zeeman shift of the asymptotic atomic states. Finally, we calculate molecular potentials using a full diagonalization approach including the p-wave contribution and all orders in the relative momentum k, and compare the obtained molecular binding energies to the experimental data.
In this work the existence of a novel type of molecule is shown whose binding is based solely on electron-atom scattering. These molecules are composed of a Rydberg atom and a ground state atom - here Rb(ns) and Rb(5s) - where the binding arises from scattering of the Rydberg electron from the ground state atom. The ground state atom is bound to the Rydberg wavefunction, which has radii on the order of 100nm, and thus these molecules are of long-range. Although the theoretical description of this interaction goes back to the famous work of Fermi in the year 1934 which was expanded in the following decades by Omont and Greene, the experimental proof of their existence was still missing. Up to now, experimental evidence for the ultralong-range Rydberg molecules was found only in spectral line broadenings. The present experiments have demonstrated the direct photoassociation of these ultralong-range Rydberg molecules for Rb(ns)-Rb(5s) triplet states from a cold and dense sample of rubidium 87 atoms for a range of principal quantum numbers, n, between 34 and 40. The high-resolution photoassociation spectra allowed for the observation of several vibrational states separated by only a few Megahertz. Based on the model by Greene the vibrational ground states v=0 are assigned and the dependence of their binding energy on the principal quantum number, n, is used to extract the triplet s-wave scattering length for electron-Rb(5s) collisions from the data. The remarkably good agreement between experiment and theory for the vibrational ground state v=0 over a range of principal quantum numbers attests to the accuracy of Fermi's original pseudopotential approach in describing interactions in excited multi-atom systems. Aside from this good agreement for the state v=0, the measurements also show that contributions from p-wave scattering cannot be neglected, as a number of excited vibrational states is observed in the experiment that are not predicted from the theory assuming only s-wave scattering. Calculations of Li, Pohl and coworkers have shown that a full solution of the electron-atom scattering is necessary for the assignment of all vibrational states. This work finds the molecular bound states to be very sensitive to both s-wave as well as p-wave electron-atom scattering and the Rydberg molecules turn out to be an accurate experimental platform to study electron-atom collisions in a previously inaccessible ultralow-energy regime. In general, the ultralong-range Rydberg molecules investigated here for rubidium are expected for all species with negative scattering length for electron-atom interaction, e. g. the other alkali atoms. Rydberg atom and ground state atom do not even have to be of the same chemical element, the only requirement is a negative scattering length of the ground state atom for electron scattering. Moreover, the binding force of the Rydberg electron is not restricted to a single ground state atom and molecules with more than one ground state atom can be created. The fact that these exotic molecules have huge bond lengths but nevertheless a vibrational spectrum with several states make a new type of ultracold Rydberg chemistry feasible. In the future, larger polymers or even heteronuclear molecules can be realized, where the number of atoms, the constituent atomic elements and the addressed Rydberg state allow to precisely select the properties of the long-range molecule.
We study angular-momentum couplings in 87Rb2 Rydberg molecules formed between a Rydberg and 5S1/2 ground-state atom. We use a Fermi model that includes S-wave and P-wave singlet and triplet scattering of the Rydberg electron with the 5S1/2 atom, along with the fine-structure coupling of the Rydberg atom and hyperfine-structure coupling of the 5S1/2 atom. We discuss the effects of these couplings on the adiabatic molecular potentials. We obtain bound-state energies, lifetimes, and electric and magnetic dipole moments for the vibrational ground states of the 87Rb(nD+5S1/2) molecules in all adiabatic potentials, with fine and hyperfine structure included. The hyperfine structure gives rise to mixed singlet-triplet potentials. We also study the effect of the hyperfine structure on the deep 3S-wave- and 3P-wave-dominated adiabatic molecular potentials, which support high-$\ensuremath{\ell}$ 87Rb2 Rydberg molecules.
Molecular bonds can be divided into four primary types: ionic, covalent, van der Waals and hydrogen bonds. At ultralow temperatures a novel binding type emerges paving the way for novel molecules and ultracold chemistry [1,2]. The underlying mechanism for this new type of chemical bond is low-energy electron scattering of Rydberg electrons from polarisable ground state atoms [3]. This quantum scattering process can generate an attractive potential that is able to bind the ground state atom to the Rydberg atom at a well localized position within the Rydberg electron wave function. The resulting giant molecules can have an internuclear separation of several thousand Bohr radii, which places them among the largest known molecules to date. Their binding energies are much smaller than the Kepler frequencies of the Rydberg electrons i.e. the atomic Rydberg electron state is essentially unchanged by the bound ground state atom. Ultracold and dense samples of atoms enable the creation of these molecules via Rydberg excitation. In this paper we present spectroscopic evidence for the vibrational ground and first excited state of a Rubidium dimer Rb(5S)-Rb(nS). We apply a Born-Oppenheimer model to explain the measured binding energies for principal quantum numbers n between 34 and 40 and extract the s-wave scattering length for electron-Rb(5S) scattering in the relevant low energy regime Ekin < 100 meV. We also determine the lifetimes and the polarisabilities of these molecules. P-wave bound states [2], Trimer states [4] as well as bound states for large angular momentum of the Rydberg electron - socalled trilobite molecules [1] - are within reach in the near future and will further refine our conceptual understanding of the chemical bond.
We observe the formation of long-range Cs2 Rydberg molecules consisting of a Rydberg and a ground-state atom by photoassociation spectroscopy in an ultracold Cs gas near 6s1/2(F=3,4)→np3/2 resonances (n=26-34). The spectra reveal two types of molecular states recently predicted by D. A. Anderson, S. A. Miller, and G. Raithel [Phys. Rev. A 90, 062518 (2014)]: states bound purely by triplet s-wave scattering with binding energies ranging from 400 MHz at n=26 to 80 MHz at n=34, and states bound by mixed singlet-triplet s-wave scattering with smaller and F-dependent binding energies. The experimental observations are accounted for by an effective Hamiltonian including s-wave scattering pseudopotentials, the hyperfine interaction of the ground-state atom, and the spin-orbit interaction of the Rydberg atom. The analysis enables the characterization of the role of singlet scattering in the formation of long-range Rydberg molecules and the determination of an effective singlet s-wave scattering length for low-energy-electron-Cs collisions.
We model the binding energies of rovibrational levels of the RbYb molecule using experimental data from two-color photoassociation spectroscopy in mixtures of ultracold 87Rb with various Yb isotopes. The model uses a theoretical potential based on state-of-the-art ab initio potentials, further improved by least-squares fitting to the experimental data. We have fixed the number of bound states supported by the potential curve, so that the model is mass scaled, that is, it accurately describes the bound-state energies for all measured isotopic combinations. Such a model enables an accurate prediction of the s-wave scattering lengths of all isotopic combinations of the RbYb system. The reduced mass range is broad enough to cover the full scattering lengths range from $\ensuremath{-}\ensuremath{\infty}$ to $+\ensuremath{\infty}$. For example, the 87Rb174Yb system is characterized by a large positive scattering length of +880(120) a.u., while 87Rb173Yb has $a=\ensuremath{-}626(88)$ a.u. On the other hand 87Rb170Yb has a very small scattering length of $\ensuremath{-}11.5(2.5)$ a.u. confirmed by the pair's extremely low thermalization rate. For isotopic combinations including 85Rb the variation of the interspecies scattering lengths is much smoother ranging from +39.0(1.6) a.u. for 85Rb176Yb to +230(12) a.u. in the case of 85Rb168Yb. Hyperfine corrections to these scattering lengths are also given. We further complement the fitted potential with interaction parameters calculated from alternative methods. The recommended value of the van der Waals coefficient is C6=2837(13) a.u. agrees with but is more precise than the current state-of-the-art theoretical predictions [M. S. Safronova, S. G. Porsev, and C. W. Clark, Phys. Rev. Lett. 109, 230802 (2012)].