Structural and Electronic properties of transition metal thiophosphates

Journal Article · Sun Nov 01 04:00:00 EST 1987 · J. Solid State Chem.; (United States)

DOI:https://doi.org/10.1016/0022-4596(87)90165-4· OSTI ID:5419134

Evain, M; Brec, R; Whangbo, M H

From the viewpoint of metal coordination the authors examine the structural characteristics of several new members of transition metal thiophosphates (i.e., M-P-S phases with M = V, Nb, Ta), in which various ligands such as S/sup 2 -/, S/sup 2 -//sub 2/, and phosphorus-sulfur polyanions P/sub n/S/sub m/sup x-/ (1 less than or equal to n less than or equal to4; 3 less than or equal to m less than or equal to 13; 2 less than or equal to x less than or equal to 6) provide either an octahedral or a bicapped prismatic coordination of the metal. Tight-binding band electronic structure calculations show that the low-lying acceptore orbitals responsible for lithium intercalation of thiophosphates are their d-block bands. This prediction is confirmed by our electrochemical lithium intercalation study which reveals that the reduction sites of thiophosphates are their metal cations. Molecular orbital calculations are carried out on vanadium compounds with extremely short interligand S...S contacts. The occurrence of such short contact distances is not caused by covalent bonding in the S...S contacts but by the small size of vanadium cations which forces its surrounding sulfur ligands to squeeze one another.

• Research Organization: Universite de Nantes, France
• OSTI ID: 5419134
• Journal Information: J. Solid State Chem.; (United States), Journal Name: J. Solid State Chem.; (United States) Vol. 71:1; ISSN JSSCB
• Country of Publication: United States
• Language: English

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