Packing core-corona particles on a spherical surface.

We explore the non-trivial structures that can be obtained by the assembly of repulsive core-corona particles confined on a spherical surface. Using Monte Carlo simulations, we study the low-temperature equilibrium configurations as a function of the size of the confining (spherical) surface for a small number of particles (N ≤ 12) and obtain a large variety of minimal-energy arrangements including anisotropic and chiral structures. For a small cluster (N = 4), we construct a phase diagram in the confining surface radius vs corona range plane that showed regions where configurations with a certain energy are not accessible. Also, a phase diagram in the temperature and confining surface radius plane showed the presence of reentrant phases. The assembly of Platonic and Archimedean solids and the emergence of helical structures are also discussed. When the number of particles is large (N ≥ 100), apart from the appearance of defects, the overall configurations correspond closely to the ones formed in an unconfined two-dimensional case. Interestingly, the present model reproduces the symmetry of experimentally obtained small clusters of colloidal spheres confined at the surface of evaporating liquid droplets which cannot be explained in terms of packing of hard spheres. Thus, our simulations provide insight on the role that the softness of the particles may have in the assembly of clusters of nanoparticles.

Hybrid ADFT Study of the C104 and C106 IPR Isomers.

This work presents a hybrid auxiliary density functional theory (ADFT) study of the neutral and hexaanionic C104 and C106 fullerenes with the aim to determine their ground state structures. To this end, all C104 and C106 fullerene structures that obey the isolated pentagon rule (IPR) were optimized with the Perdew-Burke-Ernzerhof generalized gradient approximation followed by a single-point energy calculation with the PBE0 hybrid functional. Our studies show that this composite approach yields relative energies of giant fullerenes that are accurate to around 1 kcal/mol. As a result, the ground states of C104, C1046-, and C1066- can be assigned to the isomers 234:Cs, 821:D2, and 891:Cs, respectively. On the other hand, the energetically lowest lying IPR isomers of C106, 331:Cs, 1194:C2, 534:C1 are separated by less than 1 kcal/mol which makes an unequivocal ground state assignment by hybrid DFT methods impossible. To guide future experiments, we also report the simulated IR and Raman spectra of the most stable neutral and hexaanionic C104 and C106 fullerenes.