Electronic and magnetic properties of endohedrally doped fullerene Mn@C60: A total energy study

Abstract

We perform total energy calculations on a manganese atom encapsulated inside a C 60 cage using density functional theory with the generalized gradient approximation through three optimization schemes and along four paths inside the cage. We find that when Mn is located in the central region, its electronic and magnetic properties are not exactly the same as those of a free Mn atom due to weak coupling between Mn and the cage. As Mn is shifted toward to the edge, the total energy and spin start to change significantly when Mn is situated about one-third of the way between the cage center and edge, and the total energy reaches a local minimum. Finally the interaction between Mn and the cage turns repulsive as Mn approaches the edge. We also find that, along the lowest energy path, there exist three consecutive local energy minima and each of these has a different spin M. The ground state has the lowest M = 3, Mn is located about 1.6 Å away from the cage center, and the binding energy is 0.08 eV. We attribute the decrease in total energy and spin to Mn and C hybridization.

Electron transfer and localization in endohedral metallofullerenes:Ab initiodensity functional theory calculations

“…9 This charge delocalization picture seems to be supported by experimental 10 and theoretical studies. 11 Even in studies showing strong metal-fullerene hybridization, [12][13][14][15][16][17] the transferred charge is considered to be primarily delocalized over the cage. Thus, metallofullerenes have been regarded as "superatoms" 2 or stable ion pairs 18 that consist of a positively charged metal core surrounded by a homogeneously negatively charged carbon cage.…”

Noble Gases Encaged by the C60 Increase Their Chemical Reactivity

“…Without doubt, the confinement exerted on quantum systems has given unexpected trends on chemical and physical properties of the matter. The confinement imposed by fullerenes or nanotubes is a hot topic nowadays since it opens possible technological applications [1][2][3][4][5][6][7][8][9][10]. One way to study the electronic structure of systems encaged by fullerenes is by solving the Kohn-Sham [11] or Hartree-Fock [12] equations for the whole system; the fullerene (host) plus the corresponding enclosed guest.…”

Exploring the Surface Reactivity of 3d Metal Endofullerenes: A Density-Functional Theory Study

“…To the best of our knowledge, there are only a few reports on the synthesis (or attempts to synthesize) and characterization of unconventional endofullerenes with late 3d transition metal atoms (groups 7−12 of the Periodic Table). ,− However, recently, some companies have started to produce and commercialize some of these new endohedral metallofullerenes at very low costs, − making them attractive materials for experimental research and industrial applications. Theoretical studies have an important role to investigate the structural and electronic properties of this type of endofullerene and predict their striking characteristics. − …”