Negative thermal expansion and low-frequency modes in cyanide-bridged framework materials

被引：314

作者：

Goodwin, AL

Kepert, CJ

机构：

[1] Univ Cambridge, Dept Earth Sci, Cambridge CB2 3EQ, England

[2] Univ Sydney, Sch Chem, Sydney, NSW 2006, Australia

来源：

PHYSICAL REVIEW B | 2005年 / 71卷 / 14期

关键词：

D O I：

10.1103/PhysRevB.71.140301

中图分类号：

T [工业技术];

学科分类号：

08 ;

摘要：

We analyze the intrinsic geometric flexibility of framework structures incorporating linear metal-cyanide-metal (M-CN-M') linkages using a reciprocal-space dynamical matrix approach. We find that this structural motif is capable of imparting a significant negative thermal expansion (NTE) effect upon such materials. In particular, we show that the topologies of a number of simple cyanide-containing framework materials support a very large number of low-energy rigid-unit phonon modes, all of which give rise to NTE behavior. We support our analysis by presenting experimental verification of this behavior in the family of compounds ZnxCd1-x(CN)(2), which we show to exhibit a NTE effect over the temperature range 25-375 K more than double that of materials such as ZrW2O8.

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