The Frenkel Line: a direct experimental evidence for the new thermodynamic boundary

Bolmatov, Dima; Zhernenkov, Mikhail; Zav’yalov, Dmitry; Tkachev, Sergey N.; Cunsolo, Alessandro; Cai, Yong Q.

doi:10.1038/srep15850

Title: The Frenkel Line: a direct experimental evidence for the new thermodynamic boundary

Journal Article · Thu Nov 05 00:00:00 EST 2015 · Scientific Reports

DOI:https://doi.org/10.1038/srep15850· OSTI ID:1235468

Bolmatov, Dima ^[1]; Zhernenkov, Mikhail ^[1]; Zav’yalov, Dmitry ^[2]; Tkachev, Sergey N. ^[3]; Cunsolo, Alessandro ^[1]; Cai, Yong Q. ^[1]

Brookhaven National Lab. (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II)
Volgograd State Technical Univ., Volgograd (Russia)
Univ. of Chicago, IL (United States). Center for Advanced Radiation Sources (CARS)

We report that supercritical fluids play a significant role in elucidating fundamental aspects of liquid matter under extreme conditions. They have been extensively studied at pressures and temperatures relevant to various industrial applications. However, much less is known about the structural behaviour of supercritical fluids and no structural crossovers have been observed in static compression experiments in any temperature and pressure ranges beyond the critical point. The structure of supercritical state is currently perceived to be uniform everywhere on the pressure-temperature phase diagram, and to change only in a monotonic way even moving around the critical point, not only along isotherms or isobars. Conversely, we observe structural crossovers for the first time in a deeply supercritical sample through diffraction measurements in a diamond anvil cell and discover a new thermodynamic boundary on the pressure-temperature diagram. We explain the existence of these crossovers in the framework of the phonon theory of liquids using molecular dynamics simulations. The obtained results are of prime importance since they imply a global reconsideration of the mere essence of the supercritical phase. Furthermore, this discovery may pave the way to new unexpected applications and to the exploration of exotic behaviour of confined fluids relevant to geo- and planetary sciences.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0012704; FG02-94ER14466; AC02-06CH11357; EAR-0622171

OSTI ID:: 1235468

Journal Information:: Scientific Reports, Vol. 5, Issue 2015; ISSN 2045-2322

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United States

Language:: ENGLISH

Citation Metrics:

Cited by: 46 works

Citation information provided by
Web of Science

References (55)

Die Plancksche Theorie der Strahlung und die Theorie der spezifischen Wärme Einstein, Albert unkn https://doi.org/10.48644/867313382	text	January 2022
Die Plancksche Theorie der Strahlung und die Theorie der spezifischen Wärme Einstein, A. Annalen der Physik, Vol. 327, Issue 1 https://doi.org/10.1002/andp.19063270110	journal	January 1907
Equation of State in the Neighborhood of the Critical Point Widom, B. The Journal of Chemical Physics, Vol. 43, Issue 11 https://doi.org/10.1063/1.1696618	journal	December 1965
Universal scaling between structural relaxation and vibrational dynamics in glass-forming liquids and polymers Larini, L.; Ottochian, A.; De Michele, C. Nature Physics, Vol. 4, Issue 1 https://doi.org/10.1038/nphys788	journal	December 2007
Symmetry breaking gives rise to energy spectra of three states of matter Bolmatov, Dima; Musaev, Edvard T.; Trachenko, K. Scientific Reports, Vol. 3, Issue 1 https://doi.org/10.1038/srep02794	journal	September 2013
Effect of Pressure on the Viscosity of Water Bett, K. E.; Cappi, J. B. Nature, Vol. 207, Issue 4997 https://doi.org/10.1038/207620a0	journal	August 1965
Dynamic transition of supercritical hydrogen: Defining the boundary between interior and atmosphere in gas giants Trachenko, K.; Brazhkin, V. V.; Bolmatov, D. Physical Review E, Vol. 89, Issue 3 https://doi.org/10.1103/physreve.89.032126	journal	March 2014
Functional Activity of Plasmid DNA after Entry into the Atmosphere of Earth Investigated by a New Biomarker Stability Assay for Ballistic Spaceflight Experiments Thiel, Cora S.; Tauber, Svantje; Schütte, Andreas PLoS ONE, Vol. 9, Issue 11 https://doi.org/10.1371/journal.pone.0112979	journal	November 2014
“Liquid-Gas” Transition in the Supercritical Region: Fundamental Changes in the Particle Dynamics Brazhkin, V. V.; Fomin, Yu. D.; Lyapin, A. G. Physical Review Letters, Vol. 111, Issue 14 https://doi.org/10.1103/physrevlett.111.145901	journal	October 2013
Supercritical Carbon Dioxide and Its Potential as a Life-Sustaining Solvent in a Planetary Environment Budisa, Nediljko; Schulze-Makuch, Dirk Life, Vol. 4, Issue 3 https://doi.org/10.3390/life4030331	journal	August 2014
Explaining why simple liquids are quasi-universal Bacher, Andreas K.; Schrøder, Thomas B.; Dyre, Jeppe C. Nature Communications, Vol. 5, Issue 1 https://doi.org/10.1038/ncomms6424	journal	November 2014
Structural Evolution of Supercritical CO ₂ across the Frenkel Line Bolmatov, Dima; Zav’yalov, D.; Gao, M. The Journal of Physical Chemistry Letters, Vol. 5, Issue 16 https://doi.org/10.1021/jz5012127	journal	August 2014
Thermodynamic signature of growing amorphous order in glass-forming liquids Biroli, G.; Bouchaud, J. -P.; Cavagna, A. Nature Physics, Vol. 4, Issue 10 https://doi.org/10.1038/nphys1050	journal	August 2008
Comment: Characterizing dynamic length scales in glass forming liquids Flenner, Elijah; Szamel, Grzegorz arXiv https://doi.org/10.48550/arxiv.1208.6531	text	January 2012
Theory of simple classical fluids: Universality in the short-range structure Rosenfeld, Yaakov; Ashcroft, N. W. Physical Review A, Vol. 20, Issue 3 https://doi.org/10.1103/physreva.20.1208	journal	September 1979
Critical-like behaviour of glass-forming liquids Tanaka, Hajime; Kawasaki, Takeshi; Shintani, Hiroshi Nature Materials, Vol. 9, Issue 4 https://doi.org/10.1038/nmat2634	journal	February 2010
Explaining why simple liquids are quasi-universal Bacher, Andreas K.; Schrøder, Thomas B.; Dyre, Jeppe C. arXiv https://doi.org/10.48550/arxiv.1505.04061	text	January 2015
The phonon theory of liquid thermodynamics Bolmatov, D.; Brazhkin, V. V.; Trachenko, K. Scientific Reports, Vol. 2, Issue 1 https://doi.org/10.1038/srep00421	journal	May 2012
Quantitative structure factor and density measurements of high-pressure fluids in diamond anvil cells by x-ray diffraction: Argon and water Eggert, Jon H.; Weck, Gunnar; Loubeyre, Paul Physical Review B, Vol. 65, Issue 17 https://doi.org/10.1103/PhysRevB.65.174105	journal	April 2002
Fingerprints of order and disorder on the high-frequency dynamics of liquids Giordano, V. M.; Monaco, G. Proceedings of the National Academy of Sciences, Vol. 107, Issue 51 https://doi.org/10.1073/pnas.1006319107	journal	December 2010
BX90: A new diamond anvil cell design for X-ray diffraction and optical measurements Kantor, I.; Prakapenka, V.; Kantor, A. Review of Scientific Instruments, Vol. 83, Issue 12, Article No. 125102 https://doi.org/10.1063/1.4768541	journal	December 2012
Multiphase equation of state for carbon addressing high pressures and temperatures Benedict, Lorin X.; Driver, Kevin P.; Hamel, Sebastien Physical Review B, Vol. 89, Issue 22 https://doi.org/10.1103/PhysRevB.89.224109	journal	June 2014
A phonon thermodynamics approach of gold nanofluids synthesized in solution plasma Heo, YongKang; Antoaneta Bratescu, Maria; Aburaya, Daiki Applied Physics Letters, Vol. 104, Issue 11 https://doi.org/10.1063/1.4868872	journal	March 2014
Helium at elevated pressures: Quantum liquid with non-static shear rigidity Bolmatov, Dima; Brazhkin, V. V.; Trachenko, K. arXiv https://doi.org/10.48550/arxiv.1303.2031	text	January 2013
Revealing the Mechanism of the Viscous-to-Elastic Crossover in Liquids Bolmatov, Dima; Zhernenkov, Mikhail; Zav’yalov, Dmitry The Journal of Physical Chemistry Letters, Vol. 6, Issue 15 https://doi.org/10.1021/acs.jpclett.5b01338	journal	July 2015
Liquid heat capacity in the approach from the solid state: anharmonic theory Bolmatov, Dima; Trachenko, Kostya arXiv https://doi.org/10.48550/arxiv.1103.4011	text	January 2011
The Widom line as the crossover between liquid-like and gas-like behaviour in supercritical fluids Simeoni, G. G.; Bryk, T.; Gorelli, F. A. Nature Physics, Vol. 6, Issue 7 https://doi.org/10.1038/nphys1683	journal	June 2010
Temperature-induced ruby fluorescence shifts up to a pressure of 15 GPa in an externally heated diamond anvil cell Rekhi, Sandeep; Dubrovinsky, Leonid; Saxena, Surendra High Temperatures-High Pressures, Vol. 31, Issue 3 https://doi.org/10.1068/htrt161	journal	January 1999
Dynamics of Dense Supercritical Neon at the Transition from Hydrodynamical to Single-Particle Regimes Cunsolo, A.; Pratesi, G.; Ruocco, G. Physical Review Letters, Vol. 80, Issue 16 https://doi.org/10.1103/physrevlett.80.3515	journal	April 1998
Structural changes in supercritical fluids at high pressures Santoro, Mario; Gorelli, Federico A. Physical Review B, Vol. 77, Issue 21 https://doi.org/10.1103/physrevb.77.212103	journal	June 2008
Nonlinear dielectric effect in supercritical diethyl ether Drozd-Rzoska, Aleksandra; Rzoska, Sylwester J.; Martinez-Garcia, Julio Cesar The Journal of Chemical Physics, Vol. 141, Issue 9 https://doi.org/10.1063/1.4893979	journal	September 2014
Thermodynamic R-diagrams reveal solid-like fluid states Ruppeiner, George; Mausbach, Peter; May, Helge-Otmar Physics Letters A, Vol. 379, Issue 7 https://doi.org/10.1016/j.physleta.2014.12.021	journal	March 2015
Equations of State for Simple Liquids from the Gaussian Equivalent Representation Method Bolmatov, Dima Journal of Statistical Physics, Vol. 137, Issue 4 https://doi.org/10.1007/s10955-009-9874-2	journal	November 2009
Zur Theorie der spezifischen Wärmen Debye, P. Annalen der Physik, Vol. 344, Issue 14 https://doi.org/10.1002/andp.19123441404	journal	January 1912
Dynamics and Thermodynamics beyond the critical point Gorelli, F. A.; Bryk, T.; Krisch, M. Scientific Reports, Vol. 3, Issue 1 https://doi.org/10.1038/srep01203	journal	February 2013
Structure Factor and Radial Distribution Function for Liquid Argon at 85 °K Yarnell, J. L.; Katz, M. J.; Wenzel, R. G. Physical Review A, Vol. 7, Issue 6 https://doi.org/10.1103/PhysRevA.7.2130	journal	June 1973
A Kinetic Theory of Liquids Born, Max; Green, H. S. Nature, Vol. 159, Issue 4034 https://doi.org/10.1038/159251a0	journal	February 1947
Unified phonon-based approach to the thermodynamics of solid, liquid and gas states Bolmatov, Dima; Zavyalov, Dmitry; Zhernenkov, Mikhail arXiv https://doi.org/10.48550/arxiv.1512.07191	text	January 2015
Unified phonon-based approach to the thermodynamics of solid, liquid and gas states Bolmatov, Dima; Zav’yalov, Dmitry; Zhernenkov, Mikhail Annals of Physics, Vol. 363 https://doi.org/10.1016/j.aop.2015.09.018	journal	December 2015
Unitary thermodynamics from thermodynamic geometry II: Fit to a local density approximation Ruppeiner, George arXiv https://doi.org/10.48550/arxiv.1412.7771	text	January 2014
Insights into Phases of Liquid Water from Study of Its Unusual Glass-Forming Properties Angell, C. A. Science, Vol. 319, Issue 5863 https://doi.org/10.1126/science.1131939	journal	February 2008
Calorimetric measurements and first principles to study the (Ag-Li) liquid system Dębski, A.; Braga, M. H.; Gąsior, W. The Journal of Chemical Thermodynamics, Vol. 82 https://doi.org/10.1016/j.jct.2014.10.023	journal	March 2015
Helium at elevated pressures: Quantum liquid with non-static shear rigidity Bolmatov, D.; Brazhkin, V. V.; Trachenko, K. Journal of Applied Physics, Vol. 113, Issue 10 https://doi.org/10.1063/1.4795340	journal	March 2013
Viscosity of glass-forming liquids Mauro, J. C.; Yue, Y.; Ellison, A. J. Proceedings of the National Academy of Sciences, Vol. 106, Issue 47 https://doi.org/10.1073/pnas.0911705106	journal	November 2009
Thermodynamic behavior of supercritical matter Bolmatov, Dima; Brazhkin, V. V.; Trachenko, K. arXiv https://doi.org/10.48550/arxiv.1303.3153	text	January 2013
Thermodynamic behaviour of supercritical matter Bolmatov, Dima; Brazhkin, V. V.; Trachenko, K. Nature Communications, Vol. 4, Issue 1 https://doi.org/10.1038/ncomms3331	journal	August 2013
Melting Curves of Hydrogen, H2O, Helium and Argon at High Pressure. Datchi, F.; Loubeyre, P.; LeToullec, R. THE REVIEW OF HIGH PRESSURE SCIENCE AND TECHNOLOGY, Vol. 7 https://doi.org/10.4131/jshpreview.7.778	journal	January 1998
Evidence for structural crossover in the supercritical state Bolmatov, Dima; Brazhkin, V. V.; Fomin, Yu. D. The Journal of Chemical Physics, Vol. 139, Issue 23 https://doi.org/10.1063/1.4844135	journal	December 2013
High-frequency asymptotics of dielectric permittivity in supercooled liquids: Experimental data and conclusions of mode-coupling theory Kondrin, M. V. Journal of Experimental and Theoretical Physics, Vol. 119, Issue 4 https://doi.org/10.1134/S1063776114090155	journal	October 2014
Characterizing dynamic length scales in glass-forming liquids Flenner, Elijah; Szamel, Grzegorz Nature Physics, Vol. 8, Issue 10 https://doi.org/10.1038/nphys2437	journal	October 2012
Liquid heat capacity in the approach from the solid state: Anharmonic theory Bolmatov, Dima; Trachenko, Kostya Physical Review B, Vol. 84, Issue 5 https://doi.org/10.1103/PhysRevB.84.054106	journal	August 2011
The COMPRES/GSECARS gas-loading system for diamond anvil cells at the Advanced Photon Source Rivers, Mark; Prakapenka, Vitali; Kubo, Atsushi High Pressure Research, Vol. 28, Issue 3 https://doi.org/10.1080/08957950802333593	journal	September 2008
Understanding the atomic-level Green-Kubo stress correlation function for a liquid through phonons in a model crystal Levashov, V. A. Physical Review B, Vol. 90, Issue 17 https://doi.org/10.1103/PhysRevB.90.174205	journal	November 2014
Statistical Mechanics of Fluid Mixtures Kirkwood, John G. The Journal of Chemical Physics, Vol. 3, Issue 5 https://doi.org/10.1063/1.1749657	journal	May 1935
DIOPTAS : a program for reduction of two-dimensional X-ray diffraction data and data exploration Prescher, Clemens; Prakapenka, Vitali B. High Pressure Research, Vol. 35, Issue 3 https://doi.org/10.1080/08957959.2015.1059835	journal	May 2015

Cited By (10)

Supercritical fluid chromatography: From science fiction to scientific fact Hofstetter, Robert K.; Hasan, Mahmoud; Eckert, Carolin ChemTexts, Vol. 5, Issue 3 https://doi.org/10.1007/s40828-019-0087-2	journal	June 2019
Some Early Ideas on the Metric Geometry of Thermodynamics Ruppeiner, George Journal of Low Temperature Physics, Vol. 185, Issue 3-4 https://doi.org/10.1007/s10909-016-1605-x	journal	April 2016
Quantumness and state boundaries hidden in supercritical helium-4: A path integral centroid molecular dynamics study Takemoto, Ayumi; Kinugawa, Kenichi The Journal of Chemical Physics, Vol. 149, Issue 20 https://doi.org/10.1063/1.5053988	journal	November 2018
Some Early Ideas on the Metric Geometry of Thermodynamics Ruppeiner, George arXiv https://doi.org/10.48550/arxiv.1604.02569	text	January 2016
Widom line, dynamical crossover, and percolation transition of supercritical oxygen via molecular dynamics simulations Raman, Abhinav S.; Li, Huiyong; Chiew, Y. C. The Journal of Chemical Physics, Vol. 148, Issue 1 https://doi.org/10.1063/1.5002699	journal	January 2018
String-like collective motion in the α - and β -relaxation of a coarse-grained polymer melt Pazmiño Betancourt, Beatriz A.; Starr, Francis W.; Douglas, Jack F. The Journal of Chemical Physics, Vol. 148, Issue 10 https://doi.org/10.1063/1.5009442	journal	March 2018
Thermally triggered phononic gaps in liquids at THz scale Bolmatov, Dima; Zhernenkov, Mikhail; Zav’yalov, Dmitry Scientific Reports, Vol. 6, Issue 1 https://doi.org/10.1038/srep19469	journal	January 2016
Anomalous scaling of flexural phonon damping in nanoresonators with confined fluid De, Subhadeep; Aluru, Narayana R. Microsystems & Nanoengineering, Vol. 5, Issue 1 https://doi.org/10.1038/s41378-018-0041-2	journal	January 2019
Anomalous behavior of nonlinear refractive indexes of CO ₂ and Xe in supercritical states Mareev, Evgenii; Aleshkevich, Victor; Potemkin, Fedor Optics Express, Vol. 26, Issue 10 https://doi.org/10.1364/oe.26.013229	journal	January 2018
Supercritical fluid chromatography Vigdergauz, M. S.; Lobachev, A. L.; Lobacheva, I. V. Russian Chemical Reviews, Vol. 61, Issue 3 https://doi.org/10.1070/rc1992v061n03abeh000944	journal	March 1992

Similar Records

Experimental evidence of the Frenkel line in supercritical neon

Journal Article · Wed Apr 26 00:00:00 EDT 2017 · Physical Review B · OSTI ID:1235468

Prescher, C.; Fomin, Yu. D.; Prakapenka, V. B.; +3 more

Evidence for structural crossover in the supercritical state

Journal Article · Sat Dec 21 00:00:00 EST 2013 · Journal of Chemical Physics · OSTI ID:1235468

Bolmatov, Dima; Brazhkin, V. V.; Ryzhov, V. N.; +2 more

The Widom line and dynamical crossover in supercritical water: Popular water models versus experiments

Journal Article · Mon Sep 21 00:00:00 EDT 2015 · Journal of Chemical Physics · OSTI ID:1235468

Corradini, D.; Rovere, M.

Related Subjects

71 CLASSICAL AND QUANTUM MECHANICS
GENERAL PHYSICS

Title: The Frenkel Line: a direct experimental evidence for the new thermodynamic boundary

Citation Formats

References (55)

Cited By (10)

Similar Records

Related Subjects