Electronically excited rubidium atom in a helium cluster or film

We present theoretical studies of helium droplets and films doped with one electronically excited rubidium atom Rb( *) ((2)P). Diffusion and path integral Monte Carlo approaches are used to investigate the energetics and the structure of clusters containing up to 14 helium atoms. The surface of large clusters is approximated by a helium film. The nonpair additive potential energy surface is modeled using a diatomic in molecule scheme. Calculations show that the stable structure of Rb( *)He(n) consists of a seven helium atom ring centered at the rubidium, surrounded by a tirelike second solvation shell. A very different structure is obtained when performing a "vertical Monte Carlo transition." In this approach, a path integral Monte Carlo equilibration starts from the stable configuration of a rubidium atom in the electronic ground state adsorbed to the helium surface after switching to the electronically excited surface. In this case, Rb( *)He(n) relaxes to a weakly bound metastable state in which Rb( *) sits in a shallow dimple. The interpretation of the results is consistent with the recent experimental observations [G. Aubock et al., Phys. Rev. Lett. 101, 035301 (2008)].