A quantum chemical approach towards the electronically excited states of helium clusters

Abstract.

We have investigated the electronic energies of the ground and excited states of an octahedral helium cluster by quantum chemical ab initio calculations. The excited levels were calculated for the central atom for a set of different inter atomic separations. Our approach yields potential energy curves which are suited to describe a density dependence of the spectral features as previously observed in photo excitation experiments. The potential energy curves of the 2s and 2p states show a hump at $R\cong2.5$ Å caused by the strong perturbation of neighbouring atoms. The existence of this hump explains the experimentally observed blue shift and its dependence on the cluster size or density, respectively. The potential curves of the higher levels show almost constant energies. Perturbations of these levels are small, because the overlap between the Rydberg orbital and the orbitals of the surrounding atoms is small. This is the case for both small R values where the Rydberg orbital is well outside the cluster as well as for large R where the density drastically decreases. These findings coincide with the un-shifted features of small clusters observed in experiments.