Metastable doubly-charged Rydberg molecules

Abstract: H$_3^{2+}$ is a one-electron system with three positive nuclei and is known to be unstable in its electronic ground-state. We examine an analogous one-electron system composed of a $^{87}$Rb Rydberg atom interacting with a pair of cations and predict the existence of metastable vibrationally-bound states of $^{87}$Rb$_3^{2+}$. These molecules are long-range trimers whose stability rests on the presence of core-shell electrons and favourable scaling of the Rydberg atom's quadrupole moment with the principal quantum number $n$. Unlike recently observed ion-Rydberg dimers, whose binding is due to internal flipping of the Rydberg atom's dipole moment, the binding of $^{87}$Rb$_3^{2+}$ arises from the interaction of the ions with the Rydberg atom's quadrupole moment. The stability of these trimers is highly sensitive to $n$. We do not expect these states to exist below $n=24$ and for $n \leq 35$, their lifetime is limited by tunnelling of the Rydberg electron. In contrast, at very large $n$ the lifetime will be limited by tunnelling of the vibrational wavepacket. In between these limits, we expect a range of bound states at intermediate $n$ for which both tunnelling rates are smaller than the radiative decay rate of the Rydberg state.