Metal-substituted Ti 8C 12 metallocarbohedrynes: Toward less reactive clusters as building blocks of cluster-assembled materials

Cüneyt Berkdemir, A. W. Castleman, Jorge Osvaldo Sofo

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10 Scopus citations

Abstract

To form cluster-assembled materials, the clusters should have low reactivity and be characterized by a closed-shell electronic configuration with a large gap between the highest occupied and the lowest unoccupied molecular orbitals (HOMO-LUMO). Using spin-polarized density functional theory calculations, we investigate the M-substituted Ti 8C 12 metallocarbohedrynes to search for less reactive clusters as building blocks for cluster-assembled materials (M = Be, Mg, Ca, Sr, Ba and Sc, Y). The selected atoms in the correct stoichiometry would produce a metallocarbohedryne that is isoelectronic with the Ti 8C 12 2+, which has a closed-shell electronic configuration and an enhanced HOMO-LUMO gap of 1.735 eV. According to our results, the HOMO-LUMO gaps of the M-substituted Ti 8C 12 metallocarbohedrynes are in the range of 0.715-0.979 eV for the case of Be, Mg, Ca, Sr and Ba and in the range of 0.865-1.294 eV for the case of Sc and Y. Among all the M-substituted metallocarbohedrynes we consider here, one of the isomers of Ti 6Sc 2C 12 is not only energetically more favorable but also exhibits a larger HOMO-LUMO gap of 1.294 eV. This result indicates that the Ti 6Sc 2C 12(4) metallocarbohedryne should be less reactive than the Ti 8C 12 metallocarbohedryne which has a narrow HOMO-LUMO gap of 0.146 eV. Moreover, we show that the intercluster interaction between two individual Ti 6Sc 2C 12(4) metallocarbohedrynes is relatively weak compared to the Ti 8C 12 dimer. This journal is

Original languageEnglish (US)
Pages (from-to)9642-9653
Number of pages12
JournalPhysical Chemistry Chemical Physics
Volume14
Issue number27
DOIs
StatePublished - Jul 21 2012

All Science Journal Classification (ASJC) codes

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

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