Structural and electronic trends among group 15 polyhedral fullerenes

Antti J. Karttunen*, Mikko Linnolahti, Tapani A. Pakkanen

*Corresponding author for this work

Research output: Contribution to journalArticleScientificpeer-review

Abstract

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 P(888), As(540), Sb(620), and Bi(620), 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.

Original languageEnglish
Pages (from-to)413-422
Number of pages10
JournalTheoretical Chemistry Accounts
Volume129
Issue number3-5
DOIs
Publication statusPublished - Jun 2011
MoE publication typeA1 Journal article-refereed

Keywords

  • Ab initio calculations
  • Antimony
  • Arsenic
  • Bismuth
  • Phosphorus
  • Fullerenes
  • AUXILIARY BASIS-SETS
  • GAUSSIAN-BASIS SETS
  • CORRELATED MOLECULAR CALCULATIONS
  • APPROXIMATE COULOMB POTENTIALS
  • DENSITY-FUNCTIONAL METHODS
  • LASER-ABLATION SYNTHESIS
  • RING-SHAPED ALLOTROPES
  • ZETA VALENCE QUALITY
  • PHOSPHORUS CLUSTERS
  • IDENTITY APPROXIMATION

Fingerprint

Dive into the research topics of 'Structural and electronic trends among group 15 polyhedral fullerenes'. Together they form a unique fingerprint.

Cite this