Next-nearest neighbour contributions to P 2p{sub 3/2} X-ray photoelectron binding energy shifts of mixed transition-metal phosphides M{sub 1-x}M'{sub x}P with the MnP-type structure
- Department of Chemistry, University of Alberta, Edmonton, Alberta, T6G 2G2 (Canada)
X-ray photoelectron (XPS) and X-ray absorption (XANES) spectroscopic measurements have been made for several series of mixed transition-metal phosphides M{sub 1-x}M'{sub x}P (Co{sub 1-x}Mn{sub x}P, Mn{sub 1-x}V{sub x}P, and Co{sub 1-x}V{sub x}P), which adopt the MnP-type structure (M is more electronegative than M'). The P 2p binding energy shifts displayed by the mixed metal phosphide members do not follow the trend shown by the simple binary phosphides, a deviation which arises from the contribution of next-nearest neighbour effects operating on the primary photoemission site. The magnitude of this contribution can be derived from a simple charge potential model taking the metal electronegativity differences into account. It is suggested that these next-nearest neighbour contributions induce a charge transfer between the two dissimilar metals via metal-metal bonding, which modifies the Madelung potential experienced at the photoemission site. This charge transfer has been confirmed by analysis of the Co 2p XPS spectra as well as the P and Mn K-edge XANES spectra. - Graphical abstract: The mixed phosphides Co{sub 1-x}Mn{sub x}P, Mn{sub 1-x}V{sub x}P, and Co{sub 1-x}V{sub x}P with the MnP-type structure have been studied by use of XPS and XANES. The P 2p binding energies in the mixed phosphides display shifts relative to the binary phosphides that cannot be explained by interaction of the nearest neighbours alone.
- OSTI ID:
- 21049501
- Journal Information:
- Journal of Solid State Chemistry, Vol. 180, Issue 10; Other Information: DOI: 10.1016/j.jssc.2007.07.027; PII: S0022-4596(07)00310-6; Copyright (c) 2007 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved; Country of input: International Atomic Energy Agency (IAEA); ISSN 0022-4596
- Country of Publication:
- United States
- Language:
- English
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