Electronic structure of chainlike polysilane

Kyozaburo Takeda, Hiroyuki Teramae, Nobuo Matsumoto

Research output: Contribution to journalArticle

150 Citations (Scopus)

Abstract

Energy band structures are calculated for -(SiXY-)n polysilane, model compounds in which X and Y are H, Me, Et, Pr, and Ph (phenyl) substituents. Polysilane has a directly allowed type band structure, and a σ-σ* interband optical transition is allowed. Band-edge states are formed mainly of skeleton Si AOs (atomic orbitals), which results in a skeleton band gap. This skeleton band gap tends to be reduced when larger alkyl groups are substituted for side chains. The σ and σ* band-edge states are well delocalized on the skeleton axis. Polysilane with Ph side chains [poly(arylsilane)] exhibits a characteristic band-edge structure due to σ-π mixing between the Si skeleton and Ph side chains. This interaction removes the doubly degenerated Ph π-HOMO states. One state is mixed with the skeleton σ-valence band state and delocalized along the skeleton axis. The other remains strongly localized in the individual Ph side chains. However, no σ*-π* mixing occurs at the conduction band edge, and no change is seen in the conduction band structure. This results in the intrusion of unoccupied localized states in the skeleton band gap.

Original languageEnglish
Pages (from-to)8186-8190
Number of pages5
JournalJournal of the American Chemical Society
Volume108
Issue number26
Publication statusPublished - 1986
Externally publishedYes

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Polysilanes
Skeleton
Band structure
Electronic structure
Energy gap
Conduction bands
Optical transitions
Valence bands

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Takeda, K., Teramae, H., & Matsumoto, N. (1986). Electronic structure of chainlike polysilane. Journal of the American Chemical Society, 108(26), 8186-8190.

Electronic structure of chainlike polysilane. / Takeda, Kyozaburo; Teramae, Hiroyuki; Matsumoto, Nobuo.

In: Journal of the American Chemical Society, Vol. 108, No. 26, 1986, p. 8186-8190.

Research output: Contribution to journalArticle

Takeda, K, Teramae, H & Matsumoto, N 1986, 'Electronic structure of chainlike polysilane', Journal of the American Chemical Society, vol. 108, no. 26, pp. 8186-8190.
Takeda, Kyozaburo ; Teramae, Hiroyuki ; Matsumoto, Nobuo. / Electronic structure of chainlike polysilane. In: Journal of the American Chemical Society. 1986 ; Vol. 108, No. 26. pp. 8186-8190.
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