New insights into the negative thermal expansion: Direct experimental evidence for the “guitar-string” effect in cubic ScF3

Hu, Lei; Chen, Jun; Sanson, Andrea; Wu, Hui; Rodriguez, Clara Guglieri; Olivi, Luca; Ren, Yang; Fan, Longlong; Deng, Jinxia; Xing, Xianran

doi:10.1021/jacs.6b02370

New insights into the negative thermal expansion: Direct experimental evidence for the “guitar-string” effect in cubic ScF₃

Journal Article · Thu Jun 23 00:00:00 EDT 2016 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.6b02370· OSTI ID:1340686

Hu, Lei ^[1]; Chen, Jun ^[1]; Sanson, Andrea ^[2]; Wu, Hui ^[3]; Rodriguez, Clara Guglieri ^[4]; Olivi, Luca ^[4]; Ren, Yang ^[5]; Fan, Longlong ^[1]; Deng, Jinxia ^[1]; Xing, Xianran ^[1]

Univ. of Science and Technology Beijing, Beijing (China)
Univ. of Padova, Padova (Italy)
National Institute of Standards and Technology, Gaithersburg, MD (United States)
Elettra Synchrotron, Triestre (Italy)
Argonne National Lab. (ANL), Argonne, IL (United States)

The understanding of the negative thermal expansion (NTE) mechanism remains challenging but critical for the development of NTE materials. This study sheds light on NTE of ScF₃, one of the most outstanding materials with NTE. The local dynamics of ScF₃ has been investigated by a combined analysis of synchrotron-based X-ray total scattering, ex-tended X-ray absorption fine structure and neutron powder diffraction. Very interestingly, we observe that i) the Sc-F nearest-neighbor distance strongly expands with increasing temperature while the Sc-Sc next-nearest-neighbor distance contracts, ii) the thermal ellipsoids of relative vibrations be-tween Sc-F nearest-neighbors are highly elongated in the direction perpendicular to the Sc-F bond, indicating that the Sc-F bond is much softer to bend than to stretch, and iii) there is mainly dynamically transverse motion of fluorine atoms, rather than static shifts. Here, these results are the direct experimental evidence for the NTE mechanism, in which the rigid unit is not necessary for the occurrence of NTE, and the key role is played by the transverse thermal vibrations of fluorine atoms through the “guitar-string” effect.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Lab. (ANL), Argonne, IL (United States)

Sponsoring Organization:: National Natural Science Foundation of China (NSFC); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22) - Scientific User Facilities Division

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1340686

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 27 Vol. 138; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (33)

Negative Thermal Expansion in the Metal-Organic Framework Material Cu ₃ (1,3,5-benzenetricarboxylate) ₂ Wu, Yue; Kobayashi, Atsushi; Halder, Gregory J. Angewandte Chemie, Vol. 120, Issue 46 https://doi.org/10.1002/ange.200803925	journal	November 2008
The role of rigid unit modes in negative thermal expansion Tao, J. Z.; Sleight, A. W. Journal of Solid State Chemistry, Vol. 173, Issue 2 https://doi.org/10.1016/S0022-4596(03)00140-3	journal	July 2003
Toward an Understanding of the Local Origin of Negative Thermal Expansion in ZrW ₂ O ₈ : Limits and Inconsistencies of the Tent and Rigid Unit Mode Models Sanson, Andrea Chemistry of Materials, Vol. 26, Issue 12 https://doi.org/10.1021/cm501107w	journal	June 2014
Direct Observation of a Transverse Vibrational Mechanism for Negative Thermal Expansion in Zn(CN) ₂ : An Atomic Pair Distribution Function Analysis Chapman, Karena W.; Chupas, Peter J.; Kepert, Cameron J. Journal of the American Chemical Society, Vol. 127, Issue 44 https://doi.org/10.1021/ja055197f	journal	November 2005
Pronounced Negative Thermal Expansion from a Simple Structure: Cubic ScF ₃ Greve, Benjamin K.; Martin, Kenneth L.; Lee, Peter L. Journal of the American Chemical Society, Vol. 132, Issue 44 https://doi.org/10.1021/ja106711v	journal	November 2010
The Role of Spontaneous Polarization in the Negative Thermal Expansion of Tetragonal PbTiO ₃ -Based Compounds Chen, Jun; Nittala, Krishna; Forrester, Jennifer S. Journal of the American Chemical Society, Vol. 133, Issue 29 https://doi.org/10.1021/ja2046292	journal	July 2011
Giant Negative Thermal Expansion in NaZn ₁₃ -Type La(Fe, Si, Co) ₁₃ Compounds Huang, Rongjin; Liu, Yanying; Fan, Wei Journal of the American Chemical Society, Vol. 135, Issue 31 https://doi.org/10.1021/ja405161z	journal	July 2013
Systematic and Controllable Negative, Zero, and Positive Thermal Expansion in Cubic Zr _{1– x} Sn _x Mo ₂ O ₈ Tallentire, Sarah E.; Child, Felicity; Fall, Ian Journal of the American Chemical Society, Vol. 135, Issue 34 https://doi.org/10.1021/ja4060564	journal	August 2013
Zero Thermal Expansion and Ferromagnetism in Cubic Sc _{1– x} M _x F ₃ (M = Ga, Fe) over a Wide Temperature Range Hu, Lei; Chen, Jun; Fan, Longlong Journal of the American Chemical Society, Vol. 136, Issue 39 https://doi.org/10.1021/ja5077487	journal	September 2014
Giant Negative Thermal Expansion in Bonded MnCoGe-Based Compounds with Ni ₂ In-Type Hexagonal Structure Zhao, Ying-Ying; Hu, Feng-Xia; Bao, Li-Fu Journal of the American Chemical Society, Vol. 137, Issue 5 https://doi.org/10.1021/ja510693a	journal	January 2015
Metal−Organic Frameworks Provide Large Negative Thermal Expansion Behavior Han, Sang Soo; Goddard, William A. The Journal of Physical Chemistry C, Vol. 111, Issue 42 https://doi.org/10.1021/jp075389s	journal	October 2007
A century of zero expansion Mohn, Peter Nature, Vol. 400, Issue 6739 https://doi.org/10.1038/21778	journal	July 1999
A fresh twist on shrinking materials Attfield, J. Paul Nature, Vol. 480, Issue 7378 https://doi.org/10.1038/480465a	journal	December 2011
Colossal negative thermal expansion in BiNiO3 induced by intermetallic charge transfer Azuma, Masaki; Chen, Wei-tin; Seki, Hayato Nature Communications, Vol. 2, Issue 1 https://doi.org/10.1038/ncomms1361	journal	June 2011
Giant negative thermal expansion in magnetic nanocrystals Zheng, X. G.; Kubozono, H.; Yamada, H. Nature Nanotechnology, Vol. 3, Issue 12 https://doi.org/10.1038/nnano.2008.309	journal	October 2008
Negative thermal expansion in functional materials: controllable thermal expansion by chemical modifications Chen, Jun; Hu, Lei; Deng, Jinxia Chemical Society Reviews, Vol. 44, Issue 11 https://doi.org/10.1039/C4CS00461B	journal	January 2015
Negative thermal expansion materials † Evans, John S. O. Journal of the Chemical Society, Dalton Transactions, Issue 19 https://doi.org/10.1039/a904297k	journal	January 1999
Giant negative thermal expansion in Ge-doped anti-perovskite manganese nitrides Takenaka, K.; Takagi, H. Applied Physics Letters, Vol. 87, Issue 26 https://doi.org/10.1063/1.2147726	journal	December 2005
Negative thermal expansion Barrera, G. D.; Bruno, J. A. O.; Barron, T. H. K. Journal of Physics: Condensed Matter, Vol. 17, Issue 4 https://doi.org/10.1088/0953-8984/17/4/R03	journal	January 2005
Negative thermal expansion in crystals with the zincblende structure: an EXAFS study of CdTe Abd el All, N.; Dalba, G.; Diop, D. Journal of Physics: Condensed Matter, Vol. 24, Issue 11 https://doi.org/10.1088/0953-8984/24/11/115403	journal	February 2012
Extended x-ray-absorption fine-structure measurements of copper: Local dynamics, anharmonicity, and thermal expansion Fornasini, P.; a. Beccara, S.; Dalba, G. Physical Review B, Vol. 70, Issue 17 https://doi.org/10.1103/PhysRevB.70.174301	journal	November 2004
Negative thermal expansion and low-frequency modes in cyanide-bridged framework materials Goodwin, Andrew L.; Kepert, Cameron J. Physical Review B, Vol. 71, Issue 14 https://doi.org/10.1103/PhysRevB.71.140301	journal	April 2005
Negative thermal expansion in CuCl: An extended x-ray absorption fine structure study Vaccari, M.; Grisenti, R.; Fornasini, P. Physical Review B, Vol. 75, Issue 18 https://doi.org/10.1103/PhysRevB.75.184307	journal	May 2007
Negative thermal expansion in crystals with the delafossite structure: An extended x-ray absorption fine structure study of CuScO 2 and CuLaO 2 Ahmed, S. I.; Dalba, G.; Fornasini, P. Physical Review B, Vol. 79, Issue 10 https://doi.org/10.1103/PhysRevB.79.104302	journal	March 2009
Negative thermal expansion of ScF 3 : Insights from density-functional molecular dynamics in the isothermal-isobaric ensemble Lazar, Petr; Bučko, Tomáš; Hafner, Jürgen Physical Review B, Vol. 92, Issue 22 https://doi.org/10.1103/PhysRevB.92.224302	journal	December 2015
Structural Relationship between Negative Thermal Expansion and Quartic Anharmonicity of Cubic ScF 3 Li, Chen W.; Tang, Xiaoli; Muñoz, J. A. Physical Review Letters, Vol. 107, Issue 19 https://doi.org/10.1103/PhysRevLett.107.195504	journal	November 2011
Local Vibrations and Negative Thermal Expansion in ZrW 2 O 8 Bridges, F.; Keiber, T.; Juhas, P. Physical Review Letters, Vol. 112, Issue 4 https://doi.org/10.1103/PhysRevLett.112.045505	journal	January 2014
Frustrated Soft Modes and Negative Thermal Expansion in Z r W 2 O 8 Cao, D.; Bridges, F.; Kowach, G. R. Physical Review Letters, Vol. 89, Issue 21 https://doi.org/10.1103/PhysRevLett.89.215902	journal	November 2002
Negative Thermal Expansion in ZrW 2 O 8 : Mechanisms, Rigid Unit Modes, and Neutron Total Scattering Tucker, Matthew G.; Goodwin, Andrew L.; Dove, Martin T. Physical Review Letters, Vol. 95, Issue 25 https://doi.org/10.1103/PhysRevLett.95.255501	journal	December 2005
EXAFS Debye–Waller Factor and Thermal Vibrations of Crystals Dalba, G.; Fornasini, P. Journal of Synchrotron Radiation, Vol. 4, Issue 4 https://doi.org/10.1107/S0909049597006900	journal	July 1997
On EXAFS Debye-Waller factor and recent advances Fornasini, P.; Grisenti, R. Journal of Synchrotron Radiation, Vol. 22, Issue 5 https://doi.org/10.1107/S1600577515010759	journal	July 2015
Colossal Positive and Negative Thermal Expansion in the Framework Material Ag3[Co(CN)6] Goodwin, A. L.; Calleja, M.; Conterio, M. J. Science, Vol. 319, Issue 5864 https://doi.org/10.1126/science.1151442	journal	February 2008
Negative Thermal Expansion from 0.3 to 1050 Kelvin in ZrW2O8 Mary, T. A.; Evans, J. S. O.; Vogt, T. Science, Vol. 272, Issue 5258 https://doi.org/10.1126/science.272.5258.90	journal	April 1996

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