Academic literature on the topic 'Thermodynamic Anomalies -Network Forming Liquids'

Tetrahedral interactions describe the behavior of the most abundant and technologically important materials on Earth, such as water, silicon, carbon, germanium, and countless others. Despite their differences, these materials share unique common physical behaviors, such as liquid anomalies, open crystalline structures, and extremely poor glass-forming ability at ambient pressure. To reveal the physical origin of these anomalies and their link to the shape of the phase diagram, we systematically study the properties of the Stillinger–Weber potential as a function of the strength of the tetrahedral interaction λ. We uncover a unique transition to a reentrant spinodal line at low values of λ, accompanied with a change in the dynamical behavior, from non-Arrhenius to Arrhenius. We then show that a two-state model can provide a comprehensive understanding on how the thermodynamic and dynamic anomalies of this important class of materials depend on the strength of the tetrahedral interaction. Our work establishes a deep link between the shape of the phase diagram and the thermodynamic and dynamic properties through local structural ordering in liquids and hints at why water is so special among all substances.

The random first order transition theory (RFOT) describing the transition from a supercooled liquid to an ideal glass has been actively developed over the last twenty years. This theory is formulated in a way that allows a description of the transition from the initial equilibrium state to the final metastable state without considering any kinetic processes. The RFOT and its applications for real molecular systems (multicomponent liquids with various intermolecular potentials, gel systems, etc.) are widely represented in English-language sources. However, these studies are practically not described in any Russian sources. This paper presents an overview of the studies carried out in this field. REFERENCES 1. Sanditov D. S., Ojovan M. I. Relaxation aspectsof the liquid—glass transition. Uspekhi FizicheskihNauk. 2019;189(2): 113–133. DOI: https://doi.org/10.3367/ufnr.2018.04.0383192. Tsydypov Sh. B., Parfenov A. N., Sanditov D. S.,Agrafonov Yu. V., Nesterov A. S. Application of themolecular dynamics method and the excited statemodel to the investigation of the glass transition inargon. Available at: http://www.isc.nw.ru/Rus/GPCJ/Content/2006/tsydypov_32_1.pdf (In Russ.). GlassPhysics and Chemistry. 2006;32(1): 83–88. DOI: https://doi.org/10.1134/S10876596060101113. Berthier L., Witten T. A. Glass transition of densefluids of hard and compressible spheres. PhysicalReview E. 2009;80(2): 021502. DOI: https://doi.org/10.1103/PhysRevE.80.0215024. Sarkisov G. N. Molecular distribution functionsof stable, metastable and amorphous classical models.Uspekhi Fizicheskih Nauk. 2002;172(6): 647–669. DOI:https://doi.org/10.3367/ufnr.0172.200206b.06475. Hoover W. G., Ross M., Johnson K. W., HendersonD., Barker J. A., Brown, B. C. Soft-sphere equationof state. The Journal of Chemical Physics, 1970;52(10):4931–4941. DOI: https://doi.org/10.1063/1.16727286. Cape J. N., Woodcock L. V. Glass transition in asoft-sphere model. The Journal of Chemical Physics,1980;72(2): 976–985. DOI: https://doi.org/10.1063/1.4392177. Franz S., Mezard M., Parisi G., Peliti L. Theresponse of glassy systems to random perturbations:A bridge between equilibrium and off-equilibrium.Journal of Statistical Physics. 1999;97(3–4): 459–488.DOI: https://doi.org/10.1023/A:10046029063328. Marc Mezard and Giorgio Parisi. Thermodynamicsof glasses: a first principles computation. J. of Phys.:Condens. Matter. 1999;11: A157–A165.9. Berthier L., Jacquin H., Zamponi F. Microscopictheory of the jamming transition of harmonic spheres.Physical Review E, 2011;84(5): 051103. DOI: https://doi.org/10.1103/PhysRevE.84.05110310. Berthier L., Biroli, G., Charbonneau P.,Corwin E. I., Franz S., Zamponi F. Gardner physics inamorphous solids and beyond. The Journal of ChemicalPhysics. 2019;151(1): 010901. DOI: https://doi.org/10.1063/1.5097175 11. Berthier L., Ozawa M., Scalliet C. Configurationalentropy of glass-forming liquids. The Journal ofChemical Physics. 2019;150(16): 160902. DOI: https://doi.org/10.1063/1.509196112. Bomont J. M., Pastore G. An alternative schemeto find glass state solutions using integral equationtheory for the pair structure. Molecular Physics.2015;113(17–18): 2770–2775. DOI: https://doi.org/10.1080/00268976.2015.103832513. Bomont J. M., Hansen J. P., Pastore G.Hypernetted-chain investigation of the random firstordertransition of a Lennard-Jones liquid to an idealglass. Physical Review E. 2015;92(4): 042316. DOI:https://doi.org/10.1103/PhysRevE.92.04231614. Bomont J. M., Pastore G., Hansen J. P.Coexistence of low and high overlap phases in asupercooled liquid: An integral equation investigation.The Journal of Chemical Physics. 2017;146(11): 114504.DOI: https://doi.org/10.1063/1.497849915. Bomont J. M., Hansen J. P., Pastore G. Revisitingthe replica theory of the liquid to ideal glass transition.The Journal of Chemical Physics. 2019;150(15): 154504.DOI: https://doi.org/10.1063/1.508881116. Cammarota C., Seoane B. First-principlescomputation of random-pinning glass transition, glasscooperative length scales, and numerical comparisons.Physical Review B. 2016;94(18): 180201. DOI: https://doi.org/10.1103/PhysRevB.94.18020117. Charbonneau P., Ikeda A., Parisi G., Zamponi F.Glass transition and random close packing above threedimensions. Physical Review Letters. 2011;107(18):185702. DOI: https://doi.org/10.1103/PhysRevLett.107.18570218. Ikeda A., Miyazaki K. Mode-coupling theory asa mean-field description of the glass transition.Physical Review Letters. 2010;104(25): 255704. DOI:https://doi.org/10.1103/PhysRevLett.104.25570419. McCowan D. Numerical study of long-timedynamics and ergodic-nonergodic transitions in densesimple fluids. Physical Review E. 2015;92(2): 022107.DOI: https://doi.org/10.1103/PhysRevE.92.02210720. Ohtsu H., Bennett T. D., Kojima T., Keen D. A.,Niwa Y., Kawano M. Amorphous–amorphous transitionin a porous coordination polymer. ChemicalCommunications. 2017;53(52): 7060–7063. DOI:https://doi.org/10.1039/C7CC03333H21. Schmid B., Schilling R. Glass transition of hardspheres in high dimensions. Physical Review E.2010;81(4): 041502. DOI: https://doi.org/10.1103/PhysRevE.81.04150222. Parisi G., Slanina, F. Toy model for the meanfieldtheory of hard-sphere liquids. Physical Review E.2000;62(5): 6554. DOI: https://doi.org/10.1103/Phys-RevE.62.655423. Parisi G., Zamponi F. The ideal glass transitionof hard spheres. The Journal of Chemical Physics.2005;123(14): 144501. DOI: https://doi.org/10.1063/1.204150724. Parisi G., Zamponi F. Amorphous packings ofhard spheres for large space dimension. Journal ofStatistical Mechanics: Theory and Experiment. 2006;03:P03017. DOI: https://doi.org/10.1088/1742-5468/2006/03/P0301725. Parisi G., Procaccia I., Shor C., Zylberg J. Effectiveforces in thermal amorphous solids with genericinteractions. Physical Review E. 2019;99(1): 011001. DOI:https://doi.org/10.1103/PhysRevE.99.01100126. Stevenson J. D., Wolynes P. G. Thermodynamic −kinetic correlations in supercooled liquids: a criticalsurvey of experimental data and predictions of therandom first-order transition theory of glasses. TheJournal of Physical Chemistry B. 2005;109(31): 15093–15097. DOI: https://doi.org/10.1021/jp052279h27. Xia X., Wolynes P. G. Fragilities of liquidspredicted from the random first order transition theoryof glasses. Proceedings of the National Academy ofSciences. 2000;97(7): 2990–2994. DOI: https://doi.org/10.1073/pnas.97.7.299028. Kobryn A. E., Gusarov S., Kovalenko A. A closurerelation to molecular theory of solvation formacromolecules. Journal of Physics: Condensed Matter.2016; 28 (40): 404003. DOI: https://doi.org/10.1088/0953-8984/28/40/40400329. Coluzzi B. , Parisi G. , Verrocchio P.Thermodynamical liquid-glass transition in a Lennard-Jones binary mixture. Physical Review Letters.2000;84(2): 306. DOI: https://doi.org/10.1103/PhysRevLett.84.30630. Sciortino F., Tartaglia P. Extension of thefluctuation-dissipation theorem to the physical agingof a model glass-forming liquid. Physical Review Letters.2001;86(1): 107. DOI: https://doi.org/10.1103/Phys-RevLett.86.10731. Sciortino, F. One liquid, two glasses. NatureMaterials. 2002;1(3): 145–146. DOI: https://doi.org/10.1038/nmat75232. Farr R. S., Groot R. D. Close packing density ofpolydisperse hard spheres. The Journal of ChemicalPhysics. 2009;131(24): 244104. DOI: https://doi.org/10.1063/1.327679933. Barrat J. L., Biben T., Bocquet, L. From Paris toLyon, and from simple to complex liquids: a view onJean-Pierre Hansen’s contribution. Molecular Physics.2015;113(17-18): 2378–2382. DOI: https://doi.org/10.1080/00268976.2015.103184334. Gaspard J. P. Structure of Melt and Liquid Alloys.In Handbook of Crystal Growth. Elsevier; 2015. 580 p.DOI: https://doi.org/10.1016/B978-0-444-56369-9.00009-535. Heyes D. M., Sigurgeirsson H. The Newtonianviscosity of concentrated stabilized dispersions:comparisons with the hard sphere fluid. Journal ofRheology. 2004;48(1): 223–248. DOI: https://doi.org/10.1122/1.163498636. Ninarello A., Berthier L., Coslovich D. Structureand dynamics of coupled viscous liquids. MolecularPhysics. 2015;113(17-18): 2707–2715. DOI: https://doi.org/10.1080/00268976.2015.103908937. Russel W. B., Wagner N. J., Mewis J. Divergencein the low shear viscosity for Brownian hard-spheredispersions: at random close packing or the glasstransition? Journal of Rheology. 2013;57(6): 1555–1567.DOI: https://doi.org/10.1122/1.482051538. Schaefer T. Fluid dynamics and viscosity instrongly correlated fluids. Annual Review of Nuclearand Particle Science. 2014;64: 125–148. DOI: https://doi.org/10.1146/annurev-nucl-102313-02543939. Matsuoka H. A macroscopic model thatconnects the molar excess entropy of a supercooledliquid near its glass transition temperature to itsviscosity. The Journal of Chemical Physics. 2012;137(20):204506. DOI: https://doi.org/10.1063/1.476734840. de Melo Marques F. A., Angelini R., Zaccarelli E.,Farago B., Ruta B., Ruocco, G., Ruzicka B. Structuraland microscopic relaxations in a colloidal glass. SoftMatter. 2015;11(3): 466–471. DOI: https://doi.org/10.1039/C4SM02010C41. Deutschländer S., Dillmann P., Maret G., KeimP. Kibble–Zurek mechanism in colloidal monolayers.Proceedings of the National Academy of Sciences.2015;112(22): 6925–6930. DOI: https://doi.org/10.1073/pnas.150076311242. Chang J., Lenhoff A. M., Sandler S. I.Determination of fluid–solid transitions in modelprotein solutions using the histogram reweightingmethod and expanded ensemble simulations. TheJournal of Chemical Physics. 2004;120(6): 3003–3014.DOI: https://doi.org/10.1063/1.163837743. Gurikov P., Smirnova I. Amorphization of drugsby adsorptive precipitation from supercriticalsolutions: a review. The Journal of Supercritical Fluids.2018;132: 105–125. DOI: https://doi.org/10.1016/j.supflu.2017.03.00544. Baghel S., Cathcart H., O’Reilly N. J. Polymericamorphoussolid dispersions: areviewofamorphization, crystallization, stabilization, solidstatecharacterization, and aqueous solubilization ofbiopharmaceutical classification system class II drugs.Journal of Pharmaceutical Sciences. 2016;105(9):2527–2544. DOI: https://doi.org/10.1016/j.xphs.2015.10.00845. Kalyuzhnyi Y. V., Hlushak S. P. Phase coexistencein polydisperse multi-Yukawa hard-sphere fluid: hightemperature approximation. The Journal of ChemicalPhysics. 2006;125(3): 034501. DOI: https://doi.org/10.1063/1.221241946. Mondal C., Sengupta S. 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Liquid–liquid phase transition (LLPT) is a transition from one liquid state to another with the same composition but distinct structural change, which provides an opportunity to explore the relationships between structural transformation and thermodynamic/kinetic anomalies. Herein the abnormal endothermic LLPT in Pd43Ni20Cu27P10 glass-forming liquid was verified and studied by flash differential scanning calorimetry (FDSC) and ab initio molecular dynamics (AIMD) simulations. The results show that the change of the atomic local structure of the atoms around the Cu-P bond leads to the change in the number of specific clusters <0 2 8 0> and <1 2 5 3>, which leads to the change in the liquid structure. Our findings reveal the structural mechanisms that induce unusual heat-trapping phenomena in liquids and advance the understanding of LLPT.

Liquid water is considered to be a peculiar example of glass forming materials because of the possibility of giving rise to amorphous phases with different densities and of the thermodynamic anomalies that characterize its supercooled liquid phase. In the present work, literature data on the density of bulk liquid water are analyzed in a wide temperature-pressure range, also including the glass phases. A careful data analysis, which was performed on different density isobars, made in terms of thermodynamic response functions, like the thermal expansion αP and the specific heat differences CP−CV, proves, exclusively from the experimental data, the thermodynamic consistence of the liquid-liquid transition hypothesis. The study confirms that supercooled bulk water is a mixture of two liquid “phases”, namely the high density (HDL) and the low density (LDL) liquids that characterize different regions of the water phase diagram. Furthermore, the CP−CV isobars behaviors clearly support the existence of both a liquid–liquid transition and of a liquid–liquid critical point.

The Arrhenius crossover temperature, TA, corresponds to a thermodynamic state wherein the atomistic dynamics of a liquid becomes heterogeneous and cooperative; and the activation barrier of diffusion dynamics becomes temperature-dependent at temperatures below TA. The theoretical estimation of this temperature is difficult for some types of materials, especially silicates and borates. In these materials, self-diffusion as a function of the temperature T is reproduced by the Arrhenius law, where the activation barrier practically independent on the temperature T. The purpose of the present work was to establish the relationship between the Arrhenius crossover temperature TA and the physical properties of liquids directly related to their glass-forming ability. Using a machine learning model, the crossover temperature TA was calculated for silicates, borates, organic compounds and metal melts of various compositions. The empirical values of the glass transition temperature Tg, the melting temperature Tm, the ratio of these temperatures Tg/Tm and the fragility index m were applied as input parameters. It has been established that the temperatures Tg and Tm are significant parameters, whereas their ratio Tg/Tm and the fragility index m do not correlate much with the temperature TA. An important result of the present work is the analytical equation relating the temperatures Tg, Tm and TA, and that, from the algebraic point of view, is the equation for a second-order curved surface. It was shown that this equation allows one to correctly estimate the temperature TA for a large class of materials, regardless of their compositions and glass-forming abilities.

Abstract Empty liquids represent a wide class of materials whose constituents arrange in a random network through reversible bonds. Many key insights on the physical properties of empty liquids have originated almost independently from the study of colloidal patchy particles on one side, and a large body of theoretical and experimental research on water on the other side. Patchy particles represent a family of coarse-grained potentials that allows for a precise control of both the geometric and the energetic aspects of bonding, while water has arguably the most complex phase diagram of any pure substance, and a puzzling amorphous phase behavior. It was only recently that the exchange of ideas from both fields has made it possible to solve long-standing problems and shed new light on the behavior of empty liquids. Here we highlight the connections between patchy particles and water, focusing on the modelling principles that make an empty liquid behave like water, including the factors that control the appearance of thermodynamic and dynamic anomalies, the possibility of liquid–liquid phase transitions, and the crystallization of open crystalline structures.

Understanding in a unified manner the generic and chemically specific aspects of activated dynamics in diverse glass-forming liquids over 14 or more decades in time is a grand challenge in condensed matter physics, physical chemistry, and materials science and engineering. Large families of conceptually distinct models have postulated a causal connection with qualitatively different “order parameters” including various measures of structure, free volume, thermodynamic properties, short or intermediate time dynamics, and mechanical properties. Construction of a predictive theory that covers both the noncooperative and cooperative activated relaxation regimes remains elusive. Here, we test using solely experimental data a recent microscopic dynamical theory prediction that although activated relaxation is a spatially coupled local–nonlocal event with barriers quantified by local pair structure, it can also be understood based on the dimensionless compressibility via an equilibrium statistical mechanics connection between thermodynamics and structure. This prediction is found to be consistent with observations on diverse fragile molecular liquids under isobaric and isochoric conditions and provides a different conceptual view of the global relaxation map. As a corollary, a theoretical basis is established for the structural relaxation time scale growing exponentially with inverse temperature to a high power, consistent with experiments in the deeply supercooled regime. A criterion for the irrelevance of collective elasticity effects is deduced and shown to be consistent with viscous flow in low-fragility inorganic network-forming melts. Finally, implications for relaxation in the equilibrated deep glass state are briefly considered.

AbstractThe fundamental relationships between the structure and properties of liquids are far from being well understood. For instance, the structural origins of many liquid anomalies still remain unclear, but liquid-liquid transitions (LLT) are believed to hold a key. However, experimental demonstrations of LLTs have been rather challenging. Here, we report experimental and theoretical evidence of a second-order-like LLT in molten tin, one which favors a percolating covalent bond network at high temperatures. The observed structural transition originates from the fluctuating metallic/covalent behavior of atomic bonding, and consequently a new paradigm of liquid structure emerges. The liquid structure, described in the form of a folded network, bridges two well-established structural models for disordered systems, i.e., the random packing of hard-spheres and a continuous random network, offering a large structural midground for liquids and glasses. Our findings provide an unparalleled physical picture of the atomic arrangement for a plethora of liquids, shedding light on the thermodynamic and dynamic anomalies of liquids but also entailing far-reaching implications for studying liquid polyamorphism and dynamical transitions in liquids.

Abstract The existence of a phase transition between two distinct liquid phases in single-component network-forming liquids (e.g., water, silica, silicon) has elicited considerable scientific interest. The challenge, both for experiments and simulations, is that the liquid-liquid phase transition occurs under deeply supercooled conditions, where crystallization occurs very rapidly. Thus, early evidence from numerical equation of state studies was challenged, with the argument that slow spontaneous crystallization had been misinterpreted as evidence of a second liquid state. Rigorous free energy calculations have subsequently confirmed the existence of a liquid-liquid phase transition in some models of water, and exciting new experimental evidence has since supported these computational results. Similar results have so far not been found for silicon. Here, we present results from free energy calculations performed for silicon modelled with the classical, empirical Stillinger-Weber potential. Through a careful study employing state-of-the-art constrained simulation protocols and numerous checks for thermodynamic consistency, we find that there are two distinct metastable liquid states and a phase transition. Our results resolve a long-standing debate concerning the existence of a liquid-liquid transition in supercooled liquid silicon and address key questions regarding the nature of the phase transition and the associated critical point.