Relative concentrations of six isomeric Eu@C 72 -one based on the IPR C 72 cage (i.e., obeying the isolated-pentagon rule, IPR), two cages with a pentagon-pentagon junction (symmetries C 2 and C 2 v ), a cage with one heptagon, a cage with two heptagons, and a cage with two pentagon-pentagon fusions-are DFT computed using the Gibbs energy in a broad temperature interval. It is shown that the two non-IPR isomers with one pentagon-pentagon junction prevail at any relevant temperature and exhibit comparable populations. The IPR-satisfying structure is disfavored by both energy and entropy.

Department of Chemistry and Biochemistry University of Arizona Tucson AZ 85721 0041 USA

Department of Physical and Macromolecular Chemistry Faculty of Science Charles University Albertov 6 128 43 Praha 2 Czech Republic

Fukui Institute for Fundamental Chemistry Kyoto University Kyoto 606 8103 Japan

State Key Laboratory of Materials Processing and Die and Mould Technology School of Material Science and Engineering Huazhong University of Science and Technology Wuhan 430074 China

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