Mg@C 72 MNDO/d evaluation of the isomeric composition

Abstract

Temperature development of the relative stabilities of isomers of Mg@C 72 (which has not yet been isolated) is computed using the recently introduced MNDO/d method. Four isomers originally considered for the Ca@C 72 case are treated: one isolated-pentagon-rule (IPR) structure, two structures with a pair of adjacent pentagons, and one cage with a heptagon. The IPR structure comes as the lowest in MNDO/d potential energy, being rather closely followed by the two structures with a pentagon–pentagon pair. On the other hand, the structure with a heptagon is located too high in potential energy to be of any experimental significance. The entropy contributions are evaluated by the MNDO/d-based partition functions so that the relative concentrations can be treated accordingly. The computations suggest that if Mg@C 72 is isolated, it should be a mixture of either two or three isomers. The prediction depends on temperature prehistory. If preparation takes place at temperatures of approximately 1000 K, two isomers should be produced. If temperatures are increased to approximately 2000 K, there will already be three isomers with significant relative concentrations. The study supplies a further interesting example of the profound role of enthalpy–entropy interplay in stabilities of isomeric fullerenic structures. © 2001 by Elsevier Science Inc.