Influence of the anion on lone pair formation in Sn(II) monochalcogenides: A DFT study

Aron Walsh, Graeme W. Watson

Research output: Contribution to journalArticle

102 Citations (Scopus)

Abstract

The electronic structure of SnO, SnS, SnSe, and SnTe in the rocksalt, litharge, and herzenbergite structures has been calculated using density functional theory. Comparison of the distorted and undistorted structures allows for an explanation of the unusual experimentally observed structural transitions seen along the Sn(II) monochalcogenides. Analysis of the electronic structure shows a strong anion dependence of the Sn(II) lone pair, with the Sn(5s) and Sn(5p) states too far apart to couple directly. However, the interaction of Sn(5s) with anion states of appropriate energy produce a filled antibonding Sn(5s)-anion p combination which allows coupling of Sn(5s) and Sn(5p) to occur, resulting in a sterically active asymmetric density on Sn. While the interaction between Sn(5s) and O(2p) is strong, interactions of Sn with S, Se, and Te become gradually weaker, resulting in less high energy 5s states and hence weaker lone pairs. The stability of the distorted structures relative to the symmetric structures of higher coordination is thereby reduced, which induces the change from highly distorted litharge SnO to highly symmetric rocksalt SnTe seen along the series.

Original languageEnglish
Pages (from-to)18868-18875
Number of pages8
JournalJournal of Physical Chemistry B
Volume109
Issue number40
DOIs
Publication statusPublished - 2005 Oct 13

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Discrete Fourier transforms
Anions
Negative ions
anions
Electronic structure
electronic structure
Electron energy levels
Density functional theory
interactions
density functional theory
energy

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Surfaces, Coatings and Films
  • Materials Chemistry

Cite this

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abstract = "The electronic structure of SnO, SnS, SnSe, and SnTe in the rocksalt, litharge, and herzenbergite structures has been calculated using density functional theory. Comparison of the distorted and undistorted structures allows for an explanation of the unusual experimentally observed structural transitions seen along the Sn(II) monochalcogenides. Analysis of the electronic structure shows a strong anion dependence of the Sn(II) lone pair, with the Sn(5s) and Sn(5p) states too far apart to couple directly. However, the interaction of Sn(5s) with anion states of appropriate energy produce a filled antibonding Sn(5s)-anion p combination which allows coupling of Sn(5s) and Sn(5p) to occur, resulting in a sterically active asymmetric density on Sn. While the interaction between Sn(5s) and O(2p) is strong, interactions of Sn with S, Se, and Te become gradually weaker, resulting in less high energy 5s states and hence weaker lone pairs. The stability of the distorted structures relative to the symmetric structures of higher coordination is thereby reduced, which induces the change from highly distorted litharge SnO to highly symmetric rocksalt SnTe seen along the series.",
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Influence of the anion on lone pair formation in Sn(II) monochalcogenides : A DFT study. / Walsh, Aron; Watson, Graeme W.

In: Journal of Physical Chemistry B, Vol. 109, No. 40, 13.10.2005, p. 18868-18875.

Research output: Contribution to journalArticle

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