B80 and B101-103 clusters: remarkable stability of the core-shell structures established by validated density functionals.

Prompted by the very recent claim that the volleyball-shaped B(80) fullerene [X. Wang, Phys. Rev. B 82, 153409 (2010)] is lower in energy than the B(80) buckyball [N. G. Szwacki, A. Sadrzadeh, and B. I. Yakobson, Phys. Rev. Lett. 98, 166804 (2007)] and core-shell structure [J. Zhao, L. Wang, F. Li, and Z. Chen, J. Phys. Chem. A 114, 9969 (2010)], and inspired by the most recent finding of another core-shell isomer as the lowest energy B(80) isomer [S. De, A. Willand, M. Amsler, P. Pochet, L. Genovese, and S. Goedecher, Phys. Rev. Lett. 106, 225502 (2011)], we carefully evaluated the performance of the density functional methods in the energetics of boron clusters and confirmed that the core-shell construction (stuffed fullerene) is thermodynamically the most favorable structural pattern for B(80). Our global minimum search showed that both B(101) and B(103) also prefer a core-shell structure and that B(103) can reach the complete core-shell configuration. We called for great attention to the theoretical community when using density functionals to investigate boron-related nanomaterials.