The origin of the stereochemically active Pb(II) lone pair: DFT calculations on PbO and PbS

Aron Walsh, Graeme W. Watson

Research output: Contribution to journalArticle

164 Citations (Scopus)

Abstract

The concept of a chemically inert but stereochemically active 6s 2 lone pair is commonly associated with Pb(II). We have performed density functional theory calculations on PbO and PbS in both the rocksalt and litharge structures which show anion dependence of the stereochemically active lone pair. PbO is more stable in litharge while PbS is not, and adopts the symmetric rocksalt structure showing no lone pair activity. Analysis of the electron density, density of states and crystal orbital overlap populations shows that the asymmetric electron density formed by Pb(II) is a direct result of anion-cation interactions. The formation has a strong dependence on the electronic states of the anion and while oxygen has the states required for interaction with Pb 6s, sulphur does not. This explains for the first time why PbO forms distorted structures and possesses an asymmetric density and PbS forms symmetric structures with no lone pair activity. This analysis shows that distorted Pb(II) structures are not the result of chemically inert, sterically active lone pairs, but instead result from asymmetric electron densities that rely on direct electronic interaction with the coordinated anions.

Original languageEnglish
Pages (from-to)1422-1428
Number of pages7
JournalJournal of Solid State Chemistry
Volume178
Issue number5
DOIs
Publication statusPublished - 2005 May 1

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Discrete Fourier transforms
Anions
Negative ions
anions
Carrier concentration
Electronic states
interactions
electronics
Sulfur
Density functional theory
Cations
sulfur
Positive ions
Oxygen
density functional theory
cations
orbitals
Crystals
oxygen
crystals

All Science Journal Classification (ASJC) codes

  • Electronic, Optical and Magnetic Materials
  • Ceramics and Composites
  • Condensed Matter Physics
  • Physical and Theoretical Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

Cite this

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The origin of the stereochemically active Pb(II) lone pair : DFT calculations on PbO and PbS. / Walsh, Aron; Watson, Graeme W.

In: Journal of Solid State Chemistry, Vol. 178, No. 5, 01.05.2005, p. 1422-1428.

Research output: Contribution to journalArticle

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