The effects of halogen elements on the opening of an icosahedral B12 framework

Research output: Contribution to journalResearch articleContributedpeer-review

Contributors

  • Liang Fa Gong - , Beijing Institute of Petrochemical Technology (Author)
  • Wei Li - , Beijing Institute of Petrochemical Technology (Author)
  • Edison Osorio - , Universidad Católica Luis Amigó (Author)
  • Xin Min Wu - , Beijing Institute of Petrochemical Technology (Author)
  • Thomas Heine - , Leipzig University, Jacobs University Bremen (Author)
  • Lei Liu - , Jacobs University Bremen, Max Planck Institute for Polymer Research (Author)

Abstract

The fully halogenated or hydrogenated B12X122- (X = H, F, Cl, Br and I) clusters are confirmed to be icosahedral. On the other hand, the bare B12 cluster is shown to have a planar structure. A previous study showed that a transformation from an icosahedron to a plane happens when 5 to 7 iodine atoms are remained [P. Farràs et al., Chem. - Eur. J. 18, 13208-13212 (2012)]. Later, the transition was confirmed to be seven iodine atoms based on an infrared spectroscopy study [M. R. Fagiania et al., Chem. Phys. Lett. 625, 48-52 (2015)]. In this study, we investigated the effects of different halogen atoms on the opening of the B12 icosahedral cage by means of density functional theory calculations. We found that the halogen elements do not have significant effects on the geometries of the clusters. The computed infrared (IR) spectra show similar representative peaks for all halogen doped clusters. Interestingly, we found a blue-shift in the IR spectra with the increase in the mass of the halogen atoms. Further, we compared the Gibbs free energies at different temperatures for different halogen atoms. The results show that the Gibbs free energy differences between open and close structures of B12X7- become larger when heavier halogen atoms are presented. This interesting finding was subsequently investigated by the energy decomposition analysis.

Details

Original languageEnglish
Article number144302
JournalJournal of Chemical Physics
Volume147
Issue number14
Publication statusPublished - 14 Oct 2017
Peer-reviewedYes
Externally publishedYes

External IDs

PubMed 29031257