Pressure-Sensitive Modeling of the Reversible Lithiation of Vacant Thiospinel (In0.5□0.5)[In1.5Sn0.5]S4

✍ Scribed by J.-P. Connerade; J.-C. Jumas; J. Olivier-Fourcade

• Publisher: Elsevier Science
• Year: 2000
• Tongue: English
• Weight: 130 KB
• Volume: 152
• Category: Article
• ISSN: 0022-4596
• DOI: 10.1006/jssc.2000.8726

✦ Synopsis

A simple atomic model is described in which lithiation appears as a reversible pressure acting on con5ned atomic species which constitute the host material. It is demonstrated, by ab initio calculations of the properties of a con5ned atom as a function of the cavity radius, that the ionization of Sn occurs in the manner which has been observed, i.e., it passes directly from Sn IV to Sn II without the appearance of Sn III . This is shown not to be the case for a con5ned atom with no d shell present, and therefore we conclude that the observed property is of atomic origin and is directly related to the high compressibility of d orbitals. Extensions of our model are suggested to include relativistic e4ects, which would enable ab initio calculations of the MoK ssbauer signals to be attempted for the lithiated compounds. This would provide an independent test of our model.