Encapsulation of small magnetic clusters in fullerene cages: A density functional theory investigation within van der Waals corrections

The encapsulation of magnetic transition-metal (TM) clusters inside carbon cages (fullerenes, nanotubes) has been of great interest due to the wide range of applications, which spread from medical sensors in magnetic resonance imaging to photonic crystals. Several theoretical studies have been reported; however, our atomistic understanding of the physical properties of encapsulated magnetic TM 3d clusters is far from satisfactory. In this work, we will report general trends, derived from density functional theory within the generalized gradient approximation proposed by Perdew, Burke, and Ernzerhof (PBE), for the encapsulation properties of the TM _m@C _n (TM = Fe, Co, Ni; m=2-6, n=60,70,80,90) systems. Furthermore, to understand the role of the van der Waals corrections to the physical properties, we employed the empirical Grimme's correction (PBE+D2). We found that both PBE and PBE+D2 functionals yield almost the same geometric parameters, magnetic and electronic properties, however, PBE+D2 strongly enhances the encapsulation energy. We found that the center of mass of the TM _m clusters is displaced towards the inside C _n surfaces, except for large TM _m clusters (m=5 and 6). For few cases, e.g., Co ₄ and Fe ₄, the encapsulation changes the putative lowest-energy structure compared to the isolated TM _m clusters. We identified few physical parameters that play an important role in the sign and magnitude of the encapsulation energy, namely, cluster size, fullerene equatorial diameter, shape, curvature of the inside C _n surface, number of TM atoms that bind directly to the inside C _n surface, and the van der Waals correction. The total magnetic moment of encapsulated TM _m clusters decreases compared with the isolated TM _m clusters, which is expected due to the hybridization of the d-p states, and strongly depends on the size and shape of the fullerene cages.