Negative Linear Compressibility and Massive Anisotropic Thermal Expansion in Methanol Monohydrate

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Science  11 Feb 2011:
Vol. 331, Issue 6018, pp. 742-746
DOI: 10.1126/science.1198640

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The vast majority of materials shrink in all directions when hydrostatically compressed; exceptions include certain metallic or polymer foam structures, which may exhibit negative linear compressibility (NLC) (that is, they expand in one or more directions under hydrostatic compression). Materials that exhibit this property at the molecular level—crystalline solids with intrinsic NLC—are extremely uncommon. With the use of neutron powder diffraction, we have discovered and characterized both NLC and extremely anisotropic thermal expansion, including negative thermal expansion (NTE) along the NLC axis, in a simple molecular crystal (the deuterated 1:1 compound of methanol and water). Apically linked rhombuses, which are formed by the bridging of hydroxyl-water chains with methyl groups, extend along the axis of NLC/NTE and lead to the observed behavior.

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