We investigate the photodissociation of helium-solvated cesium dimer cations using action spectroscopy and quantum chemical calculations. The spectrum of Cs 2 He + shows three distinct absorption bands into both bound and dissociative states. Upon solvation with further helium atoms, considerable shifts of the absorption bands are observed, exceeding 0.1 eV (850 cm À1 ) already for Cs 2 He 10 + , along with significant broadening. The shifts are highly sensitive to the character of the excited state. Our calculations show that helium atoms adsorb on the ends of Cs 2 + . The shifts are particularly pronounced if the excited state orbitals extend to the area occupied by the helium atoms. In this case, Pauli repulsion leads to a deformation of the excited state orbitals, resulting in the observed blue shift of the transition. Since the position of the weakly bound helium atoms is ill defined, Pauli repulsion also explains the broadening.Technikerstr. 25, A-6020 Innsbruck, Austria.