Abstract

Negative thermal expansion observed along the chain direction in [Pt(NH 3) 4][PtX 2(NH 3) 4](HSO 4) 4 (where X=Cl, Br) is explained from the viewpoint of the valence fluctuation of Pt atoms. Denoting the twp Pt ions in a unit cell as Pt 3−δ and Pt 3+δ, the present theory provides the contraction of Pt 3−δ−X distance and expansion of Pt 3+δ−X distance with increasing temperature leading to the overall negative thermal expansion, in agreement with experiment.

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