Geometric, electronic, and optical properties of monomer and assembly of endohedral aluminum superatomic clusters

Takeshi Iwasa, Atsushi Nakajima

Research output: Contribution to journalArticle

7 Citations (Scopus)

Abstract

Density functional computations are used to evaluate the geometric, electronic, and optical properties of endohedral aluminum clusters X@Al 12 (X = B, Al, Si, P) and their assemblies. All X@Al 12+/0/- clusters are perfect or slightly distorted icosahedral structures, with the exception of Al13+, which is highly distorted. The projected density of states (PDOS) onto the spherical harmonics of monomers clearly reveals superatom behavior and electron shell closings of F orbitals in a 40-electron species. The electronic absorption spectrum of SiAl12 is analyzed in terms of the superatom orbitals. The optimized structures of X@Al12-Y@Al12 (X-Y = Si-Si, B-P, Al-P) dimers are constructed by facing the sides of the monomers in a staggered fashion. The PDOS of the dimers mostly exhibit five hybridizations: S, P, SD, PF, and SDG. The exceptions are HOMO, which possesses a DFG hybridized character and lies between the PF and SDG regions, and LUMO, which possesses a DG hybridized character. By analyzing the simulated absorption spectra of the B@Al12-P@Al12 and Al13-P@Al12 heterodimers, charge transfers from B/Al@Al12 to P@Al12 are found in the visible region, weakly accompanying the opposite charge transfer. The heterodimers have substantial charge carriers, estimated as the difference in electron counts from the closed-shell Si@Al12, with slight charge depletions (∼0.2). The charge distributions in B@Al 12 and P@Al12 are essentially unaltered by the insertion of Si@Al12 into the heterodimer, resulting in that the heterotrimer possesses a larger dipole moment than the heterodimer.

Original languageEnglish
Pages (from-to)21551-21557
Number of pages7
JournalJournal of Physical Chemistry C
Volume117
Issue number41
DOIs
Publication statusPublished - 2013 Oct 17

ASJC Scopus subject areas

  • Electronic, Optical and Magnetic Materials
  • Energy(all)
  • Physical and Theoretical Chemistry
  • Surfaces, Coatings and Films

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