Structural and electronic trends among group 15 polyhedral fullerenes
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We have investigated the structural and electronic characteristics of tetrahedral, octahedral, and icosahedral fullerenes composed of group 15 elements phosphorus, arsenic, antimony, and bismuth. Systematic quantum chemical studies at the DFT and MP2 levels of theory were performed to obtain periodic trends for the structural principles, stabilities, and electronic properties of the elemental nanostructures. Calibration calculations for polyhedral clusters with up to 20 atoms showed the applied theoretical approaches to be in good agreement with high-level CCSD(T)/cc-pVTZ results. By studying fullerenes up to P888, As540, Sb620, and Bi620, we found their structures and stabilities to converge smoothly toward their experimental bulk counterparts. The diameters of the largest studied cages were 4.8, 3.7, 4.8, and 5.1 nm for the P, As, Sb, and Bi fullerenes, respectively. Comparisons with the experimentally known allotropes of the studied elements suggest the predicted polyhedral cages to be thermodynamically stable. All studied group 15 polyhedral fullerenes were found to be semiconducting, and density of states analysis illustrated clear periodic trends in their electronic structure. Relativistic effects become increasingly important when moving from P to Bi and taking the spin–orbit effects into account by using a two-component procedure had a significant positive effect on the relative stability of bismuth clusters.
KeywordsAb initio calculations Antimony Arsenic Bismuth Phosphorus Fullerenes
Financial support from the Finnish Funding Agency for Technology and Innovation, European Union/European Regional Development Fund (grant 70026/08), and from the Academy of Finland is gratefully acknowledged.
- 2.Greenwood NN, Earnshaw A (1997) Chemistry of the elements. Butterworth-Heineman, OxfordGoogle Scholar
- 10.Pyykko P (1979) Interpretation of secondary periodicity in the periodic system. J Chem Res S380–S381Google Scholar
- 14.Seifert G, Heine T, Fowler PW (2001) Inorganic nanotubes and fullerenes. Eur Phys J D At Mol Opt Plasma Phys 16:341–343Google Scholar
- 34.Eichkorn K, Weigend F, Treutler O, Ahlrichs R (1997) Auxiliary basis sets for main row atoms and transition metals and their use to approximate Coulomb potentials. Theor Chem Acc 97:119–124Google Scholar
- 36.Weigend F, Haeser M (1997) RI-MP2: first derivatives and global consistency. Theor Chem Acc 97:331–340Google Scholar
- 46.CFOUR, Coupled-Cluster techniques for Computational Chemistry, a quantum-chemical program package by J. F. Stanton, J. Gauss, M. E. Harding, P. G. Szalay with contributions from A. A. Auer, R. J. Bartlett, U. Benedikt, C. Berger, D. E. Bernholdt, Y. J. Bomble, L. Cheng, O. Christiansen, M. Heckert, O. Heun, C. Huber, T.-C. Jagau, D. Jonsson, J. Jusélius, K. Klein, W. J. Lauderdale, D. A. Matthews, T. Metzroth, D. P. O’Neill, D. R. Price, E. Prochnow, K. Ruud, F. Schiffmann, W. Schwalbach, S. Stopkowicz, A. Tajti, J. Vázquez, F. Wang, J. D. Watts and the integral packages MOLECULE (J. Almlöf and P. R. Taylor), PROPS (P. R. Taylor), ABACUS (T. Helgaker, H. J. Aa. Jensen, P. Jørgensen, and J. Olsen), and ECP routines by A. V. Mitin and C. van Wüllen. For the current version, see http://www.cfour.de
- 58.Bulgakov AV, Bobrenok OF, Ozerov I, Marine W, Giorgio S, Lassesson A, Campbell EEB (2004) Phosphorus cluster production by laser ablation phosphorus cluster production by laser ablation. Appl Phys A Mater Sci Process 79:1369–1372Google Scholar