Journal articles on the topic 'QUANTUM SUPERCOOLED LIQUID'

The recently developed quantum molecular dynamics method including nuclear quantum effects demonstrated that supercooled hydrogens exhibit intrinsic properties including a precursor of superfluidity which neither normal hydrogen liquid nor solid possesses.

We developed the RexPoN force field for water based entirely on quantum mechanics. It predicts the properties of water extremely accurately, withTmelt= 273.3 K (273.15 K) and properties at 298 K: ΔHvap= 10.36 kcal/mol (10.52), density = 0.9965 g/cm3(0.9965), entropy = 68.4 J/mol/K (69.9), and dielectric constant = 76.1 (78.4), where experimental values are in parentheses. Upon heating from 0.0 K (ice) to 273.0 K (still ice), the average number of strong hydrogen bonds (SHBs, rOO≤ 2.93 Å) decreases from 4.0 to 3.3, but upon melting at 273.5 K, the number of SHBs drops suddenly to 2.3, decreasing slowly to 2.1 at 298 K and 1.6 at 400 K. The lifetime of the SHBs is 90.3 fs at 298 K, increasing monotonically for lower temperature. These SHBs connect to form multibranched polymer chains (151 H2O per chain at 298 K), where branch points have 3 SHBs and termination points have 1 SHB. This dynamic fluctuating branched polymer view of water provides a dramatically modified paradigm for understanding the properties of water. It may explain the 20-nm angular correlation lengths at 298 K and the critical point at 227 K in supercooled water. Indeed, the 15% jump in the SHB lifetime at 227 K suggests that the supercooled critical point may correspond to a phase transition temperature of the dynamic polymer structure. This paradigm for water could have a significant impact on the properties for protein, DNA, and other materials in aqueous media.

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. 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Glass-forming ability is one of the most desired properties of organic compounds dedicated to optoelectronic applications. Therefore, finding general structure–property relationships and other rules governing vitrification and related near-glass-transition phenomena is a burning issue for numerous compound families, such as Schiff bases. Hence, we employ differential scanning calorimetry, broadband dielectric spectroscopy, X-ray diffraction and quantum density functional theory calculations to investigate near-glass-transition phenomena, as well as ambient- and high-pressure molecular dynamics for two structurally related Schiff bases belonging to the family of glycine imino esters. Firstly, the surprising great stability of the supercooled liquid phase is shown for these compounds, also under high-pressure conditions. Secondly, atypical self-organization via bifurcated hydrogen bonds into lasting centrosymmetric dimers is proven. Finally, by comparing the obtained results with the previous report, some general rules that govern ambient- and high-pressure molecular dynamics and near-glass transition phenomena are derived for the family of glycine imino esters. Particularly, we derive a mathematical formula to predict and tune their glass transition temperature (Tg) and its pressure coefficient (dTg/dp). We also show that, surprisingly, despite the presence of intra- and intermolecular hydrogen bonds, van der Waals and dipole–dipole interactions are the main forces governing molecular dynamics and dielectric properties of glycine imino esters.

David Chandler, a major figure in statistical mechanics, spent his career at the University of Illinois Urbana-Champaign, the University of Pennsylvania and the University of California Berkeley. Starting in his graduate work, he made significant advances in many areas of statistical mechanics theory, such as the structure and thermodynamics of simple liquids and nonpolar molecular liquids, the nature of hydrophobic hydration and hydrophobic interactions in aqueous systems, chemical reaction rates, quantum processes in liquids such as electron transfer and the solvation of an excess electron in water, ‘transition path sampling’ (a method for using computer simulations to study chemical reaction rates and other dynamic processes in liquids), and the ‘dynamic facilitation’ theory of the properties of supercooled liquids and the glass transition. He received the Hildebrand Award and the Theoretical Chemistry Award from the American Chemical Society and the Irving Langmuir Chemical Physics Award from the American Physical Society. He was elected to membership in the US National Academy of Sciences and the American Academy of Arts and Sciences.

The hypothesis that the anomalous behavior of liquid water is related to the existence of a second critical point in deeply supercooled states has long been the subject of intense debate. Recent, sophisticated experiments designed to observe the transformation between the two subcritical liquids on nano- and microsecond time scales, along with demanding numerical simulations based on classical (rigid) models parametrized to reproduce thermodynamic properties of water, have provided support to this hypothesis. A stronger numerical proof requires demonstrating that the critical point, which occurs at temperatures and pressures far from those at which the models were optimized, is robust with respect to model parameterization, specifically with respect to incorporating additional physical effects. Here we show that a liquid-liquid critical point can be rigorously located also in the WAIL model of water [J. Chem. Phys. 137, 014510 (2012)], a model parameterized using ab-initio calculations only. The model incorporates two features not present in many previously-studied water models: it is both flexible and polarizable, properties which can significantly influence the phase behavior of water. The observation of the critical point in a model in which the water-water interaction is estimated using only quantum ab-initio calculations provides strong support to the viewpoint according to which the existence of two distinct liquids is a robust feature in the free energy landscape of supercooled water.

The possible existence of a liquid–liquid critical point in deeply supercooled water has been a subject of debate due to the challenges associated with providing definitive experimental evidence. The pioneering work by Mishima and Stanley [Nature 392, 164–168 (1998)] sought to shed light on this problem by studying the melting curves of different ice polymorphs and their metastable continuation in the vicinity of the expected liquid–liquid transition and its associated critical point. Based on the continuous or discontinuous changes in the slope of the melting curves, Mishima [Phys. Rev. Lett. 85, 334 (2000)] suggested that the liquid–liquid critical point lies between the melting curves of ice III and ice V. We explore this conjecture using molecular dynamics simulations with a machine learning model based on ab initio quantum-mechanical calculations. We study the melting curves of ices III, IV, V, VI, and XIII and find that all of them are supercritical and do not intersect the liquid–liquid transition locus. We also find a pronounced, yet continuous, change in the slope of the melting lines upon crossing of the liquid locus of maximum compressibility. Finally, we analyze the literature in light of our findings and conclude that the scenario in which the melting curves are supercritical is favored by the most recent computational and experimental evidence. Although the preponderance of evidence is consistent with the existence of a second critical point in water, the behavior of ice polymorph melting lines does not provide strong evidence in support of this viewpoint, according to our calculations.

AbstractWe perform path-integral molecular dynamics (PIMD), ring-polymer MD (RPMD), and classical MD simulations of H$$_2$$ 2 O and D$$_2$$ 2 O using the q-TIP4P/F water model over a wide range of temperatures and pressures. The density $$\rho (T)$$ ρ ( T ) , isothermal compressibility $$\kappa _T(T)$$ κ T ( T ) , and self-diffusion coefficients D(T) of H$$_2$$ 2 O and D$$_2$$ 2 O are in excellent agreement with available experimental data; the isobaric heat capacity $$C_P(T)$$ C P ( T ) obtained from PIMD and MD simulations agree qualitatively well with the experiments. Some of these thermodynamic properties exhibit anomalous maxima upon isobaric cooling, consistent with recent experiments and with the possibility that H$$_2$$ 2 O and D$$_2$$ 2 O exhibit a liquid-liquid critical point (LLCP) at low temperatures and positive pressures. The data from PIMD/MD for H$$_2$$ 2 O and D$$_2$$ 2 O can be fitted remarkably well using the Two-State-Equation-of-State (TSEOS). Using the TSEOS, we estimate that the LLCP for q-TIP4P/F H$$_2$$ 2 O, from PIMD simulations, is located at $$P_c = 167 \pm 9$$ P c = 167 ± 9 MPa, $$T_c = 159 \pm 6$$ T c = 159 ± 6 K, and $$\rho _c = 1.02 \pm 0.01$$ ρ c = 1.02 ± 0.01 g/cm$$^3$$ 3 . Isotope substitution effects are important; the LLCP location in q-TIP4P/F D$$_2$$ 2 O is estimated to be $$P_c = 176 \pm 4$$ P c = 176 ± 4 MPa, $$T_c = 177 \pm 2$$ T c = 177 ± 2 K, and $$\rho _c = 1.13 \pm 0.01$$ ρ c = 1.13 ± 0.01 g/cm$$^3$$ 3 . Interestingly, for the water model studied, differences in the LLCP location from PIMD and MD simulations suggest that nuclear quantum effects (i.e., atoms delocalization) play an important role in the thermodynamics of water around the LLCP (from the MD simulations of q-TIP4P/F water, $$P_c = 203 \pm 4$$ P c = 203 ± 4 MPa, $$T_c = 175 \pm 2$$ T c = 175 ± 2 K, and $$\rho _c = 1.03 \pm 0.01$$ ρ c = 1.03 ± 0.01 g/cm$$^3$$ 3 ). Overall, our results strongly support the LLPT scenario to explain water anomalous behavior, independently of the fundamental differences between classical MD and PIMD techniques. The reported values of $$T_c$$ T c for D$$_2$$ 2 O and, particularly, H$$_2$$ 2 O suggest that improved water models are needed for the study of supercooled water.