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Article
Gd5Si4−xPx: Targeted Structural Changes through Increase in Valence Electron Count
Journal of the American Chemical Society
  • Volodymyr Svitlyk, McMaster University
  • Gordon J. Miller, Iowa State University
  • Yurij Mozharivskyj, McMaster University
Document Type
Article
Publication Version
Published Version
Publication Date
1-1-2009
DOI
10.1021/ja8085033
Abstract
Phase transformations in the Gd5Si4-xPx system (0 ≤ x ≤ 2), studied through X-ray diffraction techniques, reveal an intimate coupling between the crystal structure and valence electron count. An increase in the valence electron count through P substitution results in breaking the interslab T−T dimers (dT−T = 3.74 Å; T is a mixture of Si and P) and shear movement of the ∝2[Gd5T4] slabs in Gd5Si2.75P1.25. The Gd5Si2.75P1.25 phase extends the existence of the orthorhombic Sm5Ge4-type structures to the valence electron count larger than 31 e−/formula unit. Tight-binding linear-muffin-tin-orbital calculations trace the origin of the T−T dimer cleavage in Gd5Si2.75P1.25 to a larger population of antibonding states within the dimers.
Comments

Reprinted (adapted) with permission from J. Am. Chem. Soc., 2009, 131 (6), pp 2367–2374. Copyright 2009 American Chemical Society.

Copyright Owner
American Chemical Society
Language
en
File Format
application/pdf
Citation Information
Volodymyr Svitlyk, Gordon J. Miller and Yurij Mozharivskyj. "Gd5Si4−xPx: Targeted Structural Changes through Increase in Valence Electron Count" Journal of the American Chemical Society Vol. 131 Iss. 6 (2009) p. 2367 - 2374
Available at: http://works.bepress.com/gordon-miller/45/