Shape resonances in molecular clusters: the 2t2g shape resonances in S 2p-excited sulfur hexafluoride clusters

Sulfur hexafluoride clusters are investigated in the S 2p excitation regime. For the first time special emphasis is put on high-energy resolution spectroscopy of shape resonances in free clusters. We have investigated the 2t2g-shape resonance occurring above the S 2p threshold as one typical example to study size effects that are related to shape resonances. A small redshift of this resonance of 30 ± 5 meV occurs in clusters relative to the free molecule and changes in line shape are observed. A double-barrier optical potential model is applied for the analysis of intra- and intermolecular effects occurring in SF6 clusters, which is suitable for rationalizing the experimentally observed spectral changes. The experimental and theoretical results are briefly discussed in comparison to previous work on core-excited van der Waals clusters containing diatomic molecules.