Formation Process of Empty and Metal-Containing Fullerenes—Molecular Dynamics and FT-ICR Studies

Abstract

The formation mechanism of empty and metal-containing fullerene was studied through MD (molecular dynamics) simulations and FT-ICR (Fourier transform ion cyclotron resonance) mass spectroscopy of laser vaporized carbon cluster. Multi-body classical potential functions for metal-carbon and metal-metal interactions were constructed based on DFT (density functional theory) calculations of various forms of small clusters MCn and Mn (M = La, Sc, Ni). Using the modified Brenner potential for carbon-carbon interaction, the clustering process starting from 500 isolated carbon atoms and 5 metal atoms in gas phase was simulated under the controlled temperature condition at 3000K. The difference of clustering process of La@Cn, Sc@Cn and NiCn were compared with empty fullerene formation simulation. FT-ICR mass spectrometer directly connected to the laser vaporization cluster beam source was implemented in order to experimentally study the clustering process. The increase of cluster nozzle pressure roughly corresponded to the later stage of the molecular dynamics simulation. The FT-ICR mass spectra of metal-carbon composite clusters were compared for various sample materials used for arc-discharge generation of metal-containing fullerene and SWNT (single-wall carbon nanotube); La, Y., Sc, Gd, Ce, Ca, and Ni-Y. Positive La-C, Y-C, Sc-C, Gd-C, Ce-C binary clusters commonly showed strong MC2n+ signal in the range of 36 < 2n with intense magic numbers at MC44 +, MC50 + and MC60 +. It was speculated that the even-numbered clusters corresponded to the annealed random caged clusters observed in the MD simulation.