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Structures and negative thermal expansion properties of the one-dimensional cyanides, CuCN, AgCN and AuCN

By Simon John Hibble, Glenn B. Wood, Edward J. Bilbé, Alexander H. Pohl, Matthew G. Tucker, Alex C. Hannon and Ann Mary Chippindale


The behaviour of the lattice parameters of HTCuCN\ud (high-temperature form), AgCN and AuCN have\ud been investigated as a function of temperature over the\ud temperature range 90–490 K. All materials show one-dimensional\ud negative thermal expansion (NTE) along the\ud ––(M––CN)–– chain direction c (ac(HT-CuCN) ¼32.1\ud 10–6 K1, ac(AgCN)¼23.910–6 K1 and ac(AuCN)\ud ¼9.3106 K1 over the temperature range 90–490 K).\ud The origin of this behaviour has been studied using RMC\ud modelling of Bragg and total neutron diffraction data from\ud AgCN and AuCN at 10 and 300 K. These analyses yield\ud details of the local motions within the chains responsible for NTE. The low-temperature form of CuCN, LT-CuCN, has\ud been studied using single-crystal X-ray diffraction. In this\ud form of CuCN, wavelike distortions of the ––(Cu––CN)––\ud chains occur in the static structure, which are reminiscent\ud of the motions seen in the RMC modelling of AgCN and\ud AuCN, which are responsible for the NTE behaviour

Publisher: Oldenbourg Verlag
Year: 2010
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