A systematic study of rare gas atoms encapsulated in small fullerenes using dispersion corrected density functional theory

The most stable fullerene structures from C20 to C60 are chosen to study the energetics and geometrical consequences of encapsulating the rare gas elements He, Ne, or Ar inside the fullerene cage using dispersion corrected density functional theory. An exponential increase in stability is found with increasing number of carbon atoms. A similar exponential law is found for the volume expansion of the cage due to rare gas encapsulation with decreasing number of carbon atoms. We show that dispersion interactions become important with increasing size of the fullerene cage, where Van der Waals forces between the rare gas atom and the fullerene cage start to dominate over repulsive interactions. The smallest fullerenes where encapsulation of a rare gas element is energetically still favorable are He@C48, Ne@C52, and Ar@C58. While dispersion interactions follow the trend Ar > Ne > He inside C60 due to the trend in the rare gas dipole polarizabilities, repulsive forces become soon dominant with smaller cage size and we have a complete reversal for the energetics of rare gas encapsulation at C50. © 2014 Wiley Periodicals, Inc. Dispersion interactions are essential for a density functional treatment of rare gas encapsulation into fullerene cages. A systematic DFT study using Grimme's dispersion correction for fullerenes from C20 to C60 shows that rare gas element enclosure becomes energetically favorable only at He@C48, Ne@C52, and Ar@C58.