Comparing Empty and Filled Fullerene Cages with High-Resolution Trapped Ion Mobility Spectrometry

We have used trapped ion mobility spectrometry (TIMS) to obtain highly accurate experimental collision cross sections (CCS) for the fullerene C₈₀^- and the endohedral metallofullerenes La₂@C₈₀^-, Sc₃N@C₈₀^-, and Er₃N@C₈₀^- in molecular nitrogen. The CCS values of the endohedral fullerenes are 0.2% larger than that of the empty cage. Using a combination of density functional theory and trajectory calculations, we were able to reproduce these experimental findings theoretically. Two effects are discussed that contribute to the CCS differences: (i) a small increase in fullerene cage size upon endohedral doping and (ii) charge transfer from the encapsulated moieties to the cage thus increasing the attractive charge-induced dipole interaction between the (endohedral) fullerene ion and the nitrogen bath gas molecules.