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Local structure in Ag3[Co(CN)6]: colossal thermal expansion, rigid unit modes and argentophilic interactions

Michael J Conterio1, Andrew L Goodwin1, Matthew G Tucker2, David A Keen2,3, Martin T Dove1, Lars Peters4 and John S O Evans4

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Local structure in the colossal thermal expansion material Ag3[Co(CN)6] is studied here using a combination of neutron total scattering and reverse Monte Carlo (RMC) analysis. We show that the large thermal variations in cell dimensions occur with minimal distortion of the [Co(CN)6 ] coordination polyhedra, but involve significant flexing of the Co–CN–Ag–NC–Co linkages. We find real-space evidence in our RMC configurations for the importance of low-energy rigid unit modes (RUMs), particularly at temperatures below 150 K. Using a reciprocal-space analysis we present the phonon density of states at 300 K and show that the lowest-frequency region is dominated by RUMs and related modes. We also show that thermal variation in the energies of Ag...Ag interactions is evident in both the Ag partial pair distribution function and in the Ag partial phonon density of states. These findings are discussed in relation to the thermodynamic properties of the material.


PACS

61.66.Hq Organic compounds

65.40.De Thermal expansion; thermomechanical effects

63.20.D- Phonon states and bands, normal modes, and phonon dispersion

Subjects

Condensed matter: structural, mechanical & thermal

Dates

Issue 25 (25 June 2008)

Received 3 March 2008

Published 22 May 2008



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