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

Takeshi Iwasa, Atsushi Nakajima

Research output: Contribution to journalArticle

6 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

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Aluminum
Electronic properties
Optical properties
monomers
assembly
Monomers
aluminum
optical properties
Dimers
Electrons
Charge transfer
Absorption spectra
dimers
charge transfer
electronics
absorption spectra
orbitals
electrons
Charge distribution
Dipole moment

ASJC Scopus subject areas

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

Cite this

Geometric, electronic, and optical properties of monomer and assembly of endohedral aluminum superatomic clusters. / Iwasa, Takeshi; Nakajima, Atsushi.

In: Journal of Physical Chemistry C, Vol. 117, No. 41, 17.10.2013, p. 21551-21557.

Research output: Contribution to journalArticle

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