Scrutinizing negative thermal expansion in MOF-5 by scattering techniques and ab initio calculations

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dc.contributor.authorLock, Nen_AU
dc.contributor.authorChristensen, Men_AU
dc.contributor.authorWu, Yen_AU
dc.contributor.authorPeterson, VKen_AU
dc.contributor.authorThomsen, MKen_AU
dc.contributor.authorPiltz, ROen_AU
dc.contributor.authorRamirez-Cuesta, AJen_AU
dc.contributor.authorMcIntyre, GJen_AU
dc.contributor.authorNoren, Ken_AU
dc.contributor.authorKutteh, Ren_AU
dc.contributor.authorKepert, CJen_AU
dc.contributor.authorKearley, GJen_AU
dc.contributor.authorIversen, BBen_AU
dc.date.accessioned2013-03-13T03:08:32Zen_AU
dc.date.available2013-03-13T03:08:32Zen_AU
dc.date.issued2012-09-14en_AU
dc.date.statistics2013-03-13en_AU
dc.description.abstractComplementary experimental techniques and ab initio calculations were used to determine the origin and nature of negative thermal expansion (NTE) in the archetype metal-organic framework MOF-5 (Zn4O(1,4-benzenedicarboxylate)3). The organic linker was probed by inelastic neutron scattering under vacuum and at a gas pressure of 175 bar to distinguish between the pressure and temperature responses of the framework motions, and the local structure of the metal centers was studied by X-ray absorption spectroscopy. Multi-temperature powder- and single-crystal X-ray and neutron diffraction was used to characterize the polymeric nature of the sample and to quantify NTE over the large temperature range 4-400 K. Ab initio calculations complement the experimental data with detailed information on vibrational motions in the framework and their correlations. A uniform and comprehensive picture of NTE in MOF-5 has been drawn, and we provide direct evidence that the main contributor to NTE is translational transverse motion of the aromatic ring, which can be dampened by applying a gas pressure to the sample. The linker motion is highly correlated rather than local in nature. The relative energies of different framework vibrations populated in MOF-5 are suggested by analysis of neutron diffraction data. We note that the lowest-energy motion is a librational motion of the aromatic ring which does not contribute to NTE. The libration is followed by transverse motion of the linker and the carboxylate group. These motions result in unit-cell contraction with increasing temperature. © 2012, Royal Society of Chemistryen_AU
dc.identifier.citationLock, N., Christensen, M., Wu, Y., Peterson, V. K., Thomsen, M. K., Piltz, R. O., Ramirez-Cuesta, A. J., McIntyre, G. J., Noren, K., Kutteh, R., Kepert, C. J., Kearley, G. J., & Iversen, B. B. (2012). Scrutinizing negative thermal expansion in MOF-5 by scattering techniques and ab initio calculations. Dalton Transactions, 42(6), 1996-2007. doi:10.1039/C2DT31491Fen_AU
dc.identifier.govdoc4899en_AU
dc.identifier.issn1477-9226en_AU
dc.identifier.issue6en_AU
dc.identifier.journaltitleDalton Transactionsen_AU
dc.identifier.pagination1996-2007en_AU
dc.identifier.urihttp://dx.doi.org/10.1039/C2DT31491Fen_AU
dc.identifier.urihttp://apo.ansto.gov.au/dspace/handle/10238/4520en_AU
dc.identifier.volume42en_AU
dc.language.isoenen_AU
dc.publisherRoyal Society of Chemistryen_AU
dc.subjectScatteringen_AU
dc.subjectThermal expansionen_AU
dc.subjectMetalsen_AU
dc.subjectNeutronsen_AU
dc.subjectX-ray spectroscopyen_AU
dc.subject.otherNeutron diffractionen_AU
dc.titleScrutinizing negative thermal expansion in MOF-5 by scattering techniques and ab initio calculationsen_AU
dc.typeJournal Articleen_AU
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