Gd5Si4−xPx: Targeted Structural Changes through Increase in Valence Electron CountJournal of the American Chemical Society
Publication VersionPublished Version
AbstractPhase 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.
Copyright OwnerAmerican Chemical Society
Citation InformationVolodymyr 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/