J. Chem. Phys. 124, 204717

Nuclear magnetic resonance structural investigations of ammonia-doped fullerides
T. Shiroka, G. Fumera, O. Ligabue, and M. Riccò G. C. Antonioli

The dynamic and structural properties of the ammonia-doped superconducting fulleride (NH3)xNaK2C60 (0.5x1), well known for its anomalous decrease of transition temperature with doping, have been investigated using sodium and deuterium solid-state NMR techniques. The independence of 23Na quadrupole splitting from the ammonia content x, which, at the same time, substantially affects Tc, suggests a marginal role of the cation position in the superconducting mechanism. On the other hand, a strong reduction of the deuterium quadrupole coupling with respect to the free ammonia value denotes the presence of weak hydrogen bonds between the deuterium atoms and fullerene orbitals. Despite the bond weakness, as evinced by the lively ammonia rotational dynamics even at very low temperatures, the resulting electron localization could explain the observed Tc anomaly. The motion of the ND3–Na group (located in the compound's octahedral voids), as well as the evolution of the ammonia dynamics as a function of temperature, were determined from deuterium NMR line shape analysis and from detailed numerical simulations. While at the lowest measured temperatures only the ammonia rotation around its own C3 axis takes place, above ~25 and 70 K, respectively, also the wobbling of the C3 axis and the ND3 relocation become active, successfully modeled by a strongly correlated motion involving two different time scales