Entropic elasticity and negative thermal expansion in a simple cubic crystal

Wendt, David; Bozin, Emil; Neuefeind, Joerg; Page, Katharine; Ku, Wei; Wang, Limin; Fultz, Brent; Tkachenko, Alexei V.; Zaliznyak, Igor A.

doi:10.1126/sciadv.aay2748

Entropic elasticity and negative thermal expansion in a simple cubic crystal

Journal Article · Fri Nov 01 00:00:00 EDT 2019 · Science Advances

DOI:https://doi.org/10.1126/sciadv.aay2748· OSTI ID:1572369

Wendt, David ^[1]; Bozin, Emil ^[2]; Neuefeind, Joerg ^[3]; Page, Katharine ^[3]; Ku, Wei ^[4]; Wang, Limin ^[5]; Fultz, Brent ^[6]; Tkachenko, Alexei V. ^[2]; ^[2]

Brookhaven National Lab. (BNL), Upton, NY (United States); Island Trees High School, Levittown, NY (United States)
Brookhaven National Lab. (BNL), Upton, NY (United States)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Brookhaven National Lab. (BNL), Upton, NY (United States); Shanghai Jiao Tong Univ. (China)
Brookhaven National Lab. (BNL), Upton, NY (United States); GE Healthcare, Chicago, IL (United States)
California Inst. of Technology (CalTech), Pasadena, CA (United States)

While most solids expand when heated, some materials show the opposite behavior: negative thermal expansion (NTE). In polymers and biomolecules, NTE originates from the entropic elasticity of an ideal, freely jointed chain. The origin of NTE in solids has been widely believed to be different. Our neutron scattering study of a simple cubic NTE material, ScF₃, overturns this consensus. We observe that the correlation in the positions of the neighboring fluorine atoms rapidly fades on warming, indicating an uncorrelated thermal motion con-strained by the rigid Sc-F bonds. This leads us to a quantitative theory of NTE in terms of entropic elasticity of a floppy network crystal, which is in remarkable agreement with experimental results. We thus reveal the formidable universality of the NTE phenomenon in soft and hard matter.

View Accepted Manuscript (DOE)

Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division

Grant/Contract Number:: SC0012704

OSTI ID:: 1572369

Report Number(s):: BNL--212242-2019-JAAM

Journal Information:: Science Advances, Journal Name: Science Advances Journal Issue: 11 Vol. 5; ISSN 2375-2548

Publisher:: AAASCopyright Statement

Country of Publication:: United States

Language:: English

References (61)

The Fluoride Complexing of Scandium(III) in Aqueous Solution: Free Energies, Heats and Entropies Kury, John W.; Paul, Armine D.; Hepler, Loren G. Journal of the American Chemical Society, Vol. 81, Issue 16 https://doi.org/10.1021/ja01525a018	journal	August 1959
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
New Insights into the Negative Thermal Expansion: Direct Experimental Evidence for the “Guitar-String” Effect in Cubic ScF ₃ Hu, Lei; Chen, Jun; Sanson, Andrea Journal of the American Chemical Society, Vol. 138, Issue 27 https://doi.org/10.1021/jacs.6b02370	journal	June 2016
Errata 2: Madelung Constants of Simple Crystals Expressed in Terms of Born's Basic Potentials of 15 Figures Sakamoto, Yosio The Journal of Chemical Physics, Vol. 28, Issue 6 https://doi.org/10.1063/1.1744387	journal	June 1958
Structure of X-ray photoelectron spectra of lanthanide compounds Teterin, Yurii A.; Teterin, Anton Yu Russian Chemical Reviews, Vol. 71, Issue 5 https://doi.org/10.1070/rc2002v071n05abeh000717	journal	May 2002
On the Stability of Certain Heteropolar Crystals Evjen, H. M. Physical Review, Vol. 39, Issue 4, p. 675-687 https://doi.org/10.1103/physrev.39.675	journal	February 1932
High-resolution determination of the electron affinity of fluorine and bromine using crossed ion and laser beams Blondel, C.; Cacciani, P.; Delsart, C. Physical Review A, Vol. 40, Issue 7 https://doi.org/10.1103/physreva.40.3698	journal	October 1989
Pressure-induced cubic-to-orthorhombic phase transition in ZrW 2 O 8 Jorgensen, J. D.; Hu, Z.; Teslic, S. Physical Review B, Vol. 59, Issue 1 https://doi.org/10.1103/physrevb.59.215	journal	January 1999
Maximally localized Wannier functions for entangled energy bands Souza, Ivo; Marzari, Nicola; Vanderbilt, David Physical Review B, Vol. 65, Issue 3 https://doi.org/10.1103/physrevb.65.035109	journal	December 2001
Lattice dynamics of rhenium trioxide from the quasiharmonic approximation Wdowik, U. D.; Parlinski, K.; Chatterji, Tapan Physical Review B, Vol. 82, Issue 10 https://doi.org/10.1103/physrevb.82.104301	journal	September 2010
Large isotropic negative thermal expansion above a structural quantum phase transition Handunkanda, Sahan U.; Curry, Erin B.; Voronov, Vladimir Physical Review B, Vol. 92, Issue 13 https://doi.org/10.1103/physrevb.92.134101	journal	October 2015
Classical, quantum, and thermodynamics of a lattice model exhibiting structural negative thermal expansion Occhialini, Connor A.; Handunkanda, Sahan U.; Curry, Erin B. Physical Review B, Vol. 95, Issue 9 https://doi.org/10.1103/physrevb.95.094106	journal	March 2017
Two Decades of Negative Thermal Expansion Research: Where Do We Stand? Lind, Cora Materials, Vol. 5, Issue 12 https://doi.org/10.3390/ma5061125	journal	June 2012
Soft Manifold Dynamics Behind Negative Thermal Expansion Schlesinger, Z.; Rosen, J. A.; Hancock, J. N. arXiv https://doi.org/10.48550/arxiv.0807.1286	text	January 2008
Study of the Nature and Mechanism of the Rhombohedral-to-Cubic Phase Transition in α-AlF3 with Molecular Dynamics Simulations. Chaudhuri, Santanu; Chupas, Peter J.; Wilson, Mark ChemInform, Vol. 35, Issue 21 https://doi.org/10.1002/chin.200421002	journal	May 2004
Heat Capacity and Thermal Expansion at Low Temperatures Barron, T. H. K.; White, G. K. https://doi.org/10.1007/978-1-4615-4695-5	book	January 1999
The heat capacities of thermomiotic ScF3 and ScF3–YF3 solid solutions Romao, Carl P.; Morelock, Cody R.; Johnson, Michel B. Journal of Materials Science, Vol. 50, Issue 9 https://doi.org/10.1007/s10853-015-8899-y	journal	February 2015
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
wannier90: A tool for obtaining maximally-localised Wannier functions Mostofi, Arash A.; Yates, Jonathan R.; Lee, Young-Su Computer Physics Communications, Vol. 178, Issue 9 https://doi.org/10.1016/j.cpc.2007.11.016	journal	May 2008
Wien2wannier: From linearized augmented plane waves to maximally localized Wannier functions Kuneš, Jan; Arita, Ryotaro; Wissgott, Philipp Computer Physics Communications, Vol. 181, Issue 11 https://doi.org/10.1016/j.cpc.2010.08.005	journal	November 2010
Should Gaseous BF3 and SiF4 Be Described as Ionic Compounds? Haaland, Arne; Helgaker, Trygve; Ruud, Kenneth Journal of Chemical Education, Vol. 77, Issue 8 https://doi.org/10.1021/ed077p1076	journal	August 2000
Stepwise bond dissociation energies in sulfur hexafluoride Kiang, T.; Zare, R. N. Journal of the American Chemical Society, Vol. 102, Issue 12 https://doi.org/10.1021/ja00532a008	journal	June 1980
Study of the Nature and Mechanism of the Rhombohedral-to-Cubic Phase Transition in α-AlF ₃ with Molecular Dynamics Simulations Chaudhuri, Santanu; Chupas, Peter J.; Wilson, Mark The Journal of Physical Chemistry B, Vol. 108, Issue 11 https://doi.org/10.1021/jp034533g	journal	March 2004
Phonon density of states and negative thermal expansion in ZrW2O8 Ernst, G.; Broholm, C.; Kowach, G. R. Nature, Vol. 396, Issue 6707 https://doi.org/10.1038/24115	journal	November 1998
Applications of pair distribution function methods to contemporary problems in materials chemistry Young, Callum A.; Goodwin, Andrew L. Journal of Materials Chemistry, Vol. 21, Issue 18 https://doi.org/10.1039/c0jm04415f	journal	January 2011
Madelung Constants of Simple Crystals Expressed in Terms of Born's Basic Potentials of 15 Figures Sakamoto, Yosio The Journal of Chemical Physics, Vol. 28, Issue 1 https://doi.org/10.1063/1.1744060	journal	January 1958
The role of static disorder in negative thermal expansion in ReO3 Rodriguez, Efrain E.; Llobet, Anna; Proffen, Thomas Journal of Applied Physics, Vol. 105, Issue 11 https://doi.org/10.1063/1.3120783	journal	June 2009
Electronic structure of cubic ScF ₃ from first-principles calculations Bocharov, D.; Žguns, P.; Piskunov, S. Low Temperature Physics, Vol. 42, Issue 7 https://doi.org/10.1063/1.4959013	journal	July 2016
Structure of X-ray photoelectron spectra of lanthanide compounds Teterin, Yurii A.; Teterin, Anton Yu Russian Chemical Reviews, Vol. 71, Issue 5 https://doi.org/10.1070/RC2002v071n05ABEH000717	journal	May 2002
Negative thermal expansion and associated anomalous physical properties: review of the lattice dynamics theoretical foundation Dove, Martin T.; Fang, Hong Reports on Progress in Physics, Vol. 79, Issue 6 https://doi.org/10.1088/0034-4885/79/6/066503	journal	May 2016
Madelung constants and lattice sums for invariant cubic lattice complexes and certain tetragonal structures Zucker, I. J. Journal of Physics A: Mathematical and General, Vol. 8, Issue 11 https://doi.org/10.1088/0305-4470/8/11/008	journal	November 1975
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
Local structure in ZrW ₂ O ₈ from neutron total scattering Tucker, Matthew G.; Keen, David A.; Evans, John S. O. Journal of Physics: Condensed Matter, Vol. 19, Issue 33 https://doi.org/10.1088/0953-8984/19/33/335215	journal	July 2007
Origin of the negative thermal expansion in and Pryde, Alexandra K. A.; Hammonds, Kenton D.; Dove, Martin T. Journal of Physics: Condensed Matter, Vol. 8, Issue 50 https://doi.org/10.1088/0953-8984/8/50/023	journal	December 1996
On the Stability of Certain Heteropolar Crystals Evjen, H. M. Physical Review, Vol. 39, Issue 4, p. 675-687 https://doi.org/10.1103/PhysRev.39.675	journal	February 1932
High-resolution determination of the electron affinity of fluorine and bromine using crossed ion and laser beams Blondel, C.; Cacciani, P.; Delsart, C. Physical Review A, Vol. 40, Issue 7 https://doi.org/10.1103/PhysRevA.40.3698	journal	October 1989
Maximally localized generalized Wannier functions for composite energy bands Marzari, Nicola; Vanderbilt, David Physical Review B, Vol. 56, Issue 20 https://doi.org/10.1103/PhysRevB.56.12847	journal	November 1997
Pressure-induced cubic-to-orthorhombic phase transition in ZrW 2 O 8 Jorgensen, J. D.; Hu, Z.; Teslic, S. Physical Review B, Vol. 59, Issue 1 https://doi.org/10.1103/PhysRevB.59.215	journal	January 1999
Maximally localized Wannier functions for entangled energy bands Souza, Ivo; Marzari, Nicola; Vanderbilt, David Physical Review B, Vol. 65, Issue 3 https://doi.org/10.1103/PhysRevB.65.035109	journal	December 2001
Density-functional study of the cubic-to-rhombohedral transition in α − AlF 3 Chen, Yiing-Rei; Perebeinos, Vasili; Allen, Philip B. Physical Review B, Vol. 69, Issue 5 https://doi.org/10.1103/PhysRevB.69.054109	journal	February 2004
Empirical electronic polarizabilities in oxides, hydroxides, oxyfluorides, and oxychlorides Shannon, Robert D.; Fischer, Reinhard X. Physical Review B, Vol. 73, Issue 23 https://doi.org/10.1103/PhysRevB.73.235111	journal	June 2006
Elastic properties of a class of solids with negative thermal expansion He, Yan; Cvetkovic, Vladimir; Varma, C. M. Physical Review B, Vol. 82, Issue 1 https://doi.org/10.1103/PhysRevB.82.014111	journal	July 2010
Lattice dynamics of rhenium trioxide from the quasiharmonic approximation Wdowik, U. D.; Parlinski, K.; Chatterji, Tapan Physical Review B, Vol. 82, Issue 10 https://doi.org/10.1103/PhysRevB.82.104301	journal	September 2010
Large isotropic negative thermal expansion above a structural quantum phase transition Handunkanda, Sahan U.; Curry, Erin B.; Voronov, Vladimir Physical Review B, Vol. 92, Issue 13 https://doi.org/10.1103/PhysRevB.92.134101	journal	October 2015
Calculated hybrid and semilocal functionals and G W electronic structure of the metal trifluorides M F 3 ( M = Sc , Y, Al) Hamed, Hichem Ben; Qteish, A.; Meskini, N. Physical Review B, Vol. 92, Issue 16 https://doi.org/10.1103/PhysRevB.92.165202	journal	October 2015
Interpretation of unexpected behavior of infrared absorption spectra of ScF 3 beyond the quasiharmonic approximation Piskunov, Sergei; Žguns, Pjotrs A.; Bocharov, Dmitry Physical Review B, Vol. 93, Issue 21 https://doi.org/10.1103/PhysRevB.93.214101	journal	June 2016
Two-dimensional nanoscale correlations in the strong negative thermal expansion material ScF 3 Handunkanda, Sahan U.; Occhialini, Connor A.; Said, Ayman H. Physical Review B, Vol. 94, Issue 21 https://doi.org/10.1103/PhysRevB.94.214102	journal	December 2016
Classical, quantum, and thermodynamics of a lattice model exhibiting structural negative thermal expansion Occhialini, Connor A.; Handunkanda, Sahan U.; Curry, Erin B. Physical Review B, Vol. 95, Issue 9 https://doi.org/10.1103/PhysRevB.95.094106	journal	March 2017
Soft Manifold Dynamics behind Negative Thermal Expansion Schlesinger, Z.; Rosen, J. A.; Hancock, J. N. Physical Review Letters, Vol. 101, Issue 1 https://doi.org/10.1103/PhysRevLett.101.015501	journal	June 2008
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
Dynamics of Some Constrained Lattices Simon, M. E.; Varma, C. M. Physical Review Letters, Vol. 86, Issue 9 https://doi.org/10.1103/PhysRevLett.86.1781	journal	February 2001
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
Unusual Low-Energy Phonon Dynamics in the Negative Thermal Expansion Compound Z r W 2 O 8 Hancock, Jason N.; Turpen, Chandra; Schlesinger, Zack Physical Review Letters, Vol. 93, Issue 22 https://doi.org/10.1103/PhysRevLett.93.225501	journal	November 2004
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
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
Isotropic Negative Thermal Expansion Sleight, Arthur W. Annual Review of Materials Science, Vol. 28, Issue 1 https://doi.org/10.1146/annurev.matsci.28.1.29	journal	August 1998
wannier90: A tool for obtaining maximally-localised Wannier functions Mostofi, Arash A. Mendeley https://doi.org/10.17632/rtdryyvsxz.1	dataset	January 2019
Dynamics of Some Constrained Lattices Simon, M. E.; Varma, C. M. The American Physical Society https://doi.org/10.17877/de290r-16130	text	January 2001
The role of static disorder in negative thermal expansion in ReO3 Rodriguez, Efrain E.; Llobet, Anna; Proffen, Thomas arXiv https://doi.org/10.48550/arxiv.0812.1187	text	January 2008
Large isotropic negative thermal expansion above a structural quantum phase transition Handunkanda, Sahan U.; Curry, Erin B.; Voronov, Vladimir arXiv https://doi.org/10.48550/arxiv.1712.02865	text	January 2017
Maximally-localized Wannier functions for entangled energy bands Souza, Ivo; Marzari, Nicola; Vanderbilt, David arXiv https://doi.org/10.48550/arxiv.cond-mat/0108084	text	January 2001

Similar Records

Empty perovskites as Coulomb floppy networks: Entropic elasticity and negative thermal expansion

Journal Article · Sun Apr 11 20:00:00 EDT 2021 · Physical Review. B · OSTI ID:1782554

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

Journal Article · Wed Jun 22 20:00:00 EDT 2016 · Journal of the American Chemical Society · OSTI ID:1340686

Pronounced negative thermal expansion from a simple structure : Cubic ScF{sub 3}.

Journal Article · Tue Oct 19 00:00:00 EDT 2010 · J. Am. Chem. Soc. · OSTI ID:1001168

Related Subjects

75 CONDENSED MATTER PHYSICS
SUPERCONDUCTIVITY AND SUPERFLUIDITY

Entropic elasticity and negative thermal expansion in a simple cubic crystal

Citation Formats

References (61)

Similar Records

Related Subjects