Utilizing super-atom orbital ideas to understand properties of silver clusters inside ZSM-5 zeolite

Takashi Yumura, Mitsuhiro Kumondai, Yasushige Kuroda, Takashi Wakasugi, Hisayoshi Kobayashi

Research output: Contribution to journalArticle

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Abstract

The energetic properties of Agn clusters in ZSM-5 zeolite were investigated using density functional theory (DFT) calculations with the B3PW91 functional. Several optimized geometries (Agn-ZSM-5(Alm), 3 ≤ n ≤ 6 and 1 ≤ m ≤ 5) were obtained using this method, where m is the number of Al atoms substituted for Si atoms of a ten-membered ring of ZSM-5. DFT calculations found that an Agn cluster is well stabilized within a ZSM-5(Alm) cavity at n = m + 2. The stabilization conditions can be explained by frontier orbital theory because the HOMO of Agm+2-ZSM-5(Alm) zeolites is composed by totally symmetric 5s-based orbitals on silver atoms. The totally symmetric 5s-based orbital corresponds to a superatom S-orbital in cluster chemistry. Accordingly, the Agm+2-ZSM-5(Alm) zeolites have an S2 electronic configuration, being similar to magic-number silver clusters in the gas phase. Time-dependent DFT calculations found significant oscillator strength at the electronic transition between 5s-based orbitals from the totally symmetric orbital (S-orbital) to that with one node (P-orbital). The S → P electronic transitions in Agm+2-ZSM-5(Alm) follow the selection rule of electronic transitions of bare clusters. Because the excitation energies (λmax) change with an increase in the number of contained silver atoms, the S → P electronic transitions of Agm+2-ZSM-5(Alm) could be used to identify the state of the inner silver atoms.

Original languageEnglish
Pages (from-to)4950-4959
Number of pages10
JournalRSC Advances
Volume7
Issue number9
DOIs
Publication statusPublished - 2017

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Silver
Atoms
Density functional theory
Zeolites
Excitation energy
Electron transitions
Stabilization
Gases
ZSM-5 zeolite
Geometry

ASJC Scopus subject areas

  • Chemistry(all)
  • Chemical Engineering(all)

Cite this

Utilizing super-atom orbital ideas to understand properties of silver clusters inside ZSM-5 zeolite. / Yumura, Takashi; Kumondai, Mitsuhiro; Kuroda, Yasushige; Wakasugi, Takashi; Kobayashi, Hisayoshi.

In: RSC Advances, Vol. 7, No. 9, 2017, p. 4950-4959.

Research output: Contribution to journalArticle

Yumura, Takashi ; Kumondai, Mitsuhiro ; Kuroda, Yasushige ; Wakasugi, Takashi ; Kobayashi, Hisayoshi. / Utilizing super-atom orbital ideas to understand properties of silver clusters inside ZSM-5 zeolite. In: RSC Advances. 2017 ; Vol. 7, No. 9. pp. 4950-4959.
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