Campus Units

Chemistry

Document Type

Article

Publication Version

Published Version

Publication Date

2009

Journal or Book Title

Journal of the American Chemical Society

Volume

131

Issue

6

First Page

2367

Last Page

2374

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 TT 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 TT 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

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