Anomalous Properties Of Water Research Articles

Code for molecular dynamics simulation of two dimensional Mercedes-Benz water model

The Mercedes-Benz (MB) water model is a simple two-dimensional toy model of water that can reproduce many of the anomalous properties of water. Within the model, the water particles are represented as Lennard-Jones disks with explicitly added orientation-dependent interactions that mimic the formation of hydrogen bonds. Due to the simple implementation of the MB model in Monte Carlo simulations, it was mainly studied with Monte Carlo simulations in different ensembles. The implementation of the model in molecular dynamics simulations is not trivial. In this paper we present the code for molecular dynamics simulations. The structural and thermodynamic properties of the model were calculated using molecular dynamics and compared with data from Monte Carlo simulations to confirm that the molecular dynamics code works correctly. We also used molecular dynamics to calculate the dynamic properties of the model. The Fortran source code of our molecular dynamics simulation of the MB water model is provided.

Thermodynamics perturbation theory for solvation of nonpolar solutes in rose model.

A simple model of water, called the rose model, is used in this work. The rose model is a very simple model that can provide insight into the anomalous properties of water. In the rose water model, the molecules are represented as two-dimensional Lennard-Jones disks with potentials for orientation-dependent pairwise interactions mimicking formations of hydrogen bonds. We have recently applied a Wertheim integral equationtheory (IET) and a thermodynamic perturbation theory (TPT) to the rose model in bulk. These analytical theories offer the advantage of being computationally less intensive than computer simulations by orders of magnitudes. Here we have applied the TPT to study the transfer of a nonpolar solute into rose water, the so-called hydrophobic effect. Similarly as in our previous work for bulk water, we have found that the theory reproduces the computer simulation results quite well at higher temperatures, while the theories predict the qualitative trends at low temperatures.

Electron diffraction of deeply supercooled water in no man’s land

A generally accepted understanding of the anomalous properties of water will only emerge if it becomes possible to systematically characterize water in the deeply supercooled regime, from where the anomalies appear to emanate. This has largely remained elusive because water crystallizes rapidly between 160 K and 232 K. Here, we present an experimental approach to rapidly prepare deeply supercooled water at a well-defined temperature and probe it with electron diffraction before crystallization occurs. We show that as water is cooled from room temperature to cryogenic temperature, its structure evolves smoothly, approaching that of amorphous ice just below 200 K. Our experiments narrow down the range of possible explanations for the origin of the water anomalies and open up new avenues for studying supercooled water.

Simple rose model of water in constant electric field.

A simple two-dimensional statistical mechanical water model, called the rose model, was used in this work. We studied how a homogeneous constant electric field affects the properties of water. The rose model is a very simple model that helps explain the anomalous properties of water. Rose water molecules are represented as two-dimensional Lennard-Jones disks with potentials for orientation-dependent pairwise interactions mimicking formations of hydrogen bonds. The original model is modified by addition of charges for interaction with the electric field. We studied what kind of influence the electric field strength has on the model's properties. To determine the structure and thermodynamics of the rose model under the influence of the electric field we used Monte Carlo simulations. Under the influence of a weak electric field the anomalous properties and phase transitions of the water do not change. On the other hand, the strong fields shift the phase transition points as well as the position of the density maximum.

Subsurface Anticyclonic Eddy Transited from Kuroshio Shedding Eddy in the Northern South China Sea

Abstract Subsurface eddies are a special type of oceanic eddy that display the maximum velocity in the subsurface layer. Based on field observations, a lens-shaped subsurface anticyclonic eddy (SAE) was detected in the northern South China Sea (SCS) in May 2021. The SAE was located between 20 and 200 m, with a shoaling of the seasonal thermocline and deepening of the main thermocline. Satellite images showed that the SAE exhibited positive sea level anomaly (SLA) and negative sea surface temperature (SST) anomaly. Eddy track indicated that this SAE originated from the Luzon Strait and was generated in the Kuroshio Loop Current (KLC) last winter. The evolution of the SAE was related to the anomalous water properties inside the eddy and the seasonal change of sea surface heat flux. In winter, the continuous surface cooling and Kuroshio intrusion led to a cold, salty core in the upper part of the anticyclonic eddy, which resulted in a subsurface-intensified structure through geostrophic adjustment. As the season changed from winter to spring, sea surface temperature increased. The lens-shaped structure was formed when the seasonal thermocline appeared near the surface that capped the winter well-mixed water inside the eddy. From 1993 to 2021, nearly half of the winter KLC shedding eddies (12/25) survived to late spring and evolved into subsurface lens-shaped structures. This result indicates that the transition of KLC shedding eddy to SAE is a common phenomenon in the northern SCS, which is potentially important for local air–sea interaction, heat–salt balance, and biogeochemical processes. Significance Statement Subsurface eddies are lens-shaped eddies with anomalous water properties in the subsurface layer. While such eddies have been reported in many regions of the World Ocean, they are poorly investigated in the SCS, especially the periodic subsurface eddies that appear in a fixed time frame with similar patterns and trajectories. This study reported a subsurface anticyclonic eddy (SAE) in the northern SCS and elucidated its generation and evolution processes. Statistical results confirm that this is a periodic SAE, which occurs nearly annually in late spring and evolves from the Kuroshio shedding eddy with seasonal changes. This study provides a new perspective on the evolution of subsurface eddies in the SCS and will benefit targeted observations in the future.

Data-driven many-body potentials from density functional theory for aqueous phase chemistry

Density functional theory (DFT) has been applied to modeling molecular interactions in water for over three decades. The ubiquity of water in chemical and biological processes demands a unified understanding of its physics, from the single molecule to the thermodynamic limit and everything in between. Recent advances in the development of data-driven and machine-learning potentials have accelerated simulation of water and aqueous systems with DFT accuracy. However, anomalous properties of water in the condensed phase, where a rigorous treatment of both local and non-local many-body (MB) interactions is in order, are often unsatisfactory or partially missing in DFT models of water. In this review, we discuss the modeling of water and aqueous systems based on DFT and provide a comprehensive description of a general theoretical/computational framework for the development of data-driven many-body potentials from DFT reference data. This framework, coined MB-DFT, readily enables efficient many-body molecular dynamics (MD) simulations of small molecules, in both gas and condensed phases, while preserving the accuracy of the underlying DFT model. Theoretical considerations are emphasized, including the role that the delocalization error plays in MB-DFT potentials of water and the possibility to elevate DFT and MB-DFT to near-chemical-accuracy through a density-corrected formalism. The development of the MB-DFT framework is described in detail, along with its application in MB-MD simulations and recent extension to the modeling of reactive processes in solution within a quantum mechanics/MB molecular mechanics (QM/MB-MM) scheme, using water as a prototypical solvent. Finally, we identify open challenges and discuss future directions for MB-DFT and QM/MB-MM simulations in condensed phases.

Applying SAFT-type models for the anomalous properties of water: Successes and challenges

Water is the most important, but at the same time the most anomalous substance on earth. Due to its anomalies, it is a challenge even for advanced equations of state like PC-SAFT, CPA and SAFT-VR Mie to predict water’s anomalous properties. It is believed by some researchers that water’s anomalous properties are the result of structural fluctuations. The recently developed DAPT model is consistent with this idea and it is actually able to predict a considerable amount of water’s anomalies, like the density maximum and speed of sound maximum, which is promising, but we show in this work that it produces also some unrealistic results like minima and maxima for isochoric heat capacity. Also DAPT’s accuracy falls at high temperatures/high pressure regions where water behaves like a simple fluid. This reveals further the complexity of the problem since a successful model should treat water as an anomalous and as a simple fluid when necessary. Moreover, all of the association models fail to reproduce some of water’s structural properties and especially the tetrahedral fraction. It may be that a more accurate structural representation of water and the inclusion of steric hindrance and cooperativity effects could provide a more realistic model for water.

Dynamical Behavior of Water; Fluctuation, Reactions and Phase Transitions

Abstract Water dynamical and thermodynamical properties in molecular scale were theoretically investigated in a wide range of temperatures to clarify the physical origin of anomalous water properties. It was found in water that there exist intermittent and collective motions that arise from hydrogen bond network rearrangement. These intermittent motions become more distinctive with temperature decrease and diminish at the glass transition. In a deeply supercooled region, water dynamics shows that a new (“the third”) branch exists in its relaxation and in this branch special defects, H2O1, play a critical role. These defects make water glass transition temperature remarkably low. The intermittent collective motions have significant effects on water phase transitions and chemical reactions. The detailed dynamical mechanisms of the water freezing and the ice melting processes were analyzed. It was found how the embryos of nuclei for these processes are created and grow. The fast proton transfer mechanism in ice was also investigated to find its physical origin. Due to a strong geometrical constraint in ice, the excess proton is not trapped in a deep energy minimum and makes a facile transfer on the small energy barrier surface. As for the auto-dissociation process of water molecules, non-monotonic temperature dependence was theoretically clarified in a wide range of temperatures from ambient to supercritical region. On water roles in biomolecular functions, ion/proton transports and concomitant molecular relaxations were examined in ion-channel, photoactive yellow protein and reaction center.

Enhancement and maximum in the isobaric specific-heat capacity measurements of deeply supercooled water using ultrafast calorimetry

Knowledge of the temperature dependence of the isobaric specific heat (Cp) upon deep supercooling can give insights regarding the anomalous properties of water. If a maximum in Cp exists at a specific temperature, as in the isothermal compressibility, it would further validate the liquid-liquid critical point model that can explain the anomalous increase in thermodynamic response functions. The challenge is that the relevant temperature range falls in the region where ice crystallization becomes rapid, which has previously excluded experiments. Here, we have utilized a methodology of ultrafast calorimetry by determining the temperature jump from femtosecond X-ray pulses after heating with an infrared laser pulse and with a sufficiently long time delay between the pulses to allow measurements at constant pressure. Evaporative cooling of ∼15-µm diameter droplets in vacuum enabled us to reach a temperature down to ∼228 K with a small fraction of the droplets remaining unfrozen. We observed a sharp increase in Cp, from 88 J/mol/K at 244 K to about 218 J/mol/K at 229 K where a maximum is seen. The Cp maximum is at a similar temperature as the maxima of the isothermal compressibility and correlation length. From the Cp measurement, we estimated the excess entropy and self-diffusion coefficient of water and these properties decrease rapidly below 235 K.

Subthermocline Eddies in the Kuroshio Extension Region Observed by Mooring Arrays

AbstractSubthermocline eddies (STEs), also termed intrathermocline eddies or submesoscale coherent vortices, are lens-shaped eddies with anomalous water properties located in or below the thermocline. Although STEs have been discovered in many parts of the World Ocean, most of them were observed accidentally in hydrographic profiles, and direct velocity measurements are very rare. In this study, dynamic features of STEs in the Kuroshio Extension (KE) region are examined in detail using concurrent temperature/salinity and velocity measurements from mooring arrays. During the moored observation periods of 2004–06 and 2015–19, 11 single-core STEs, including 8 with warm/salty cores and 3 with cold/fresh cores, were captured. The thermohaline properties in their cores suggest that these STEs may originate from the subarctic front and the upstream Kuroshio south of Japan. The estimated radius of these STEs varied from 8 to 66 km with the mean value of ~30 km. The warm/salty STEs seemed to be larger and rotate faster than the cold/fresh ones. In addition to single-core STEs, a dual-core STE was observed in the KE recirculation region, which showed that the upper cold/fresh cores stacked vertically over the lower warm/salty cores. Based on the observed parameters of the STEs, their Rossby number and Burger number were further estimated, with values up to 0.5 and 1, respectively. Furthermore, a low Richardson number O (0.25) was found at the periphery of these STEs, suggesting that shear instability-induced turbulent mixing may be an erosion route for the STEs.

Evaluating the Performance of the PC-SAFT and CPA Equations of State on Anomalous Properties of Water

Water is the most important and at the same time the most anomalous substance on earth. Due to its importance, there are numerous studies concerned with the modeling of water using advanced equatio...

Understanding how water models affect the anomalous pressure dependence of their diffusion coefficients

The self-diffusion coefficient of water shows an anomalous increase with increasing hydrostatic pressure up to a broad maximum (PmD) near 1 kbar at 298 K, which has been attributed to pressure effects on the tetrahedral hydrogen bond network of water. Moreover, the ability of a water model to reproduce anomalous properties of water is a signature that it is reproducing the network. Here, water was simulated between 1 bar and 5 kbar using three water models, two four-site (with all charges in the molecular plane) and one single-site multipole (which accounts for out-of-molecular plane charge), that have reasonable pressure-temperature properties. For these three models, the diffusion coefficients display a maximum in the pressure dependence and the radial distribution functions show good agreement with the limited experimental structural data at high pressure that are available. In addition, a variety of properties associated with the network are examined, including hydrogen bond lifetimes and occupancies, three-body angle distributions, and tetrahedral order parameters. Results suggest that the initial increasing diffusion with pressure is because hydrogen bonds are distorted and thus weakened by pressure, but above PmD, the hydrogen bonds are weakened to the point it behaves more like a normal liquid. In other words, the PmD may be a measure of the angular strength of hydrogen bonds. In addition, since the four-site models over-predict the values of PmD while the multipole model under-predicts it, out-of-plane charge may improve four-site models.

Decoding a Percolation Phase Transition of Water at ∼330 K with a Nanoparticle Ruler.

Liquid water, despite its simple molecular structure, remains one of the most fascinating and complex substances. Most notably, many questions continue to exist regarding the phase transitions and anomalous properties of water, which are subtle to observe experimentally. Here, we report a sharp transition in water at 330 K unveiled through experimental measurements of the instantaneous Brownian velocity of NaYF4:Yb/Er upconversion nanoparticles in water. Our experimental investigations, corroborated by molecular dynamics simulations, elucidate a geometrical phase transition where a low-density liquid (LDL) clusters become percolated below 330 K. Around this critical temperature, we find the sizes of the LDL clusters to be similar to those of the nanoparticles, confirming the role of the upconversion nanoparticle as a powerful ruler for measuring the extensiveness of the LDL hydrogen-bond network and nanometer-scale spatial changes (20-100 nm) in liquids. Additionally, a new order parameter that unequivocally classifies water molecules into two local geometric states is introduced, providing a new tool for understanding and modeling water's many anomalous properties and phase transitions.

Anomalies in Supercooled Water at ∼230 K Arise from a 1D Polymer to 2D Network Topological Transformation.

Puzzling anomalous properties of water are drastically enhanced in the supercooled region. However, the nature of these anomalies is not known. We report here molecular dynamics simulations using the RexPoN force field from 298 to 200 K along the 1 atm density curve. At 298 K, there are 2.1 strong hydrogen bonds (SHBs), leading to a dynamic branched one-dimensional (1D) polymer. Water remains 1D down to 240 K, but at and below 230 K, the number of SHBs becomes 3.0, leading to a two-dimensional (2D) network that persists to 200 K. We propose that this 1D-to-2D topological transition accounts for the anomalous properties of supercooled water. Near 230 K, the power spectra show dramatic increases in the angular vibrational frequency modes, while the diffusivity decreases dramatically, both arising from the 1D-to-2D transformation. This transition is not first order because free energy changes uniformly but fluctuations in the entropy near 230 K suggest a possible second-order transition.

Thermodynamic properties and anomalous behavior of double-Gaussian core model potential fluids.

The structural, thermodynamic, and vapor-liquid equilibria properties of the double-Gaussian core model (DGM) potential are studied via molecular simulation. Results are presented for the pressure (p), potential energy (U), isochoric and isobaric heat capacities (C_{V,p}), isothermal compressibility (β_{T}), isochoric thermal pressure coefficient (γ_{V}), thermal expansion coefficient (α_{p}), speed of sound (ω_{0}), and the Joule-Thomson coefficient (μ_{JT}), which are compared with simulations for the Gaussian core model (GCM) potential. A feature of the simulations is that both the GCM and DGM potentials reproduce many of the anomalous properties of water, such as a maximum density, γ_{V}<0, maximum values for both α_{p} and β_{T}, and minimum values in both C_{p} and ω_{0}. The presence of attractive interaction enhances the anomalies and also yields some additional features such as a more structured vapor phase and Joule-Thomson inversion.

Is water one liquid or two?

The idea that water is a mixture of two distinct states is analyzed in some detail. It is shown that the known compressibility of water is in fact sufficiently small that for a volume of water of size 1 nm3, the density fluctuations are of order 4% of the average density. This is much smaller than the ≈25% density fluctuations that would be required for significant regions of high and low density water to occur on this volume scale. It is also pointed out that the density fluctuations in water are, if anything, smaller than those that occur in other common liquids which do not have the anomalous properties of water. It is shown that if the distribution of density fluctuations is unimodal, the system is in the one-phase region, and if bimodal, it is in the two-phase region. None of the liquid or amorphous phases of water explored in this work give any sign of being in the two-phase region. Existing neutron and X-ray scattering data on water in the amorphous phases, and in the stable liquid phases as a function pressure and temperature, are subject to a new set of empirical potential structure refinement simulations. These simulations are interrogated for their configurational entropy, using a spherical harmonic reconstruction of the full orientational pair correlation function. It is shown that the excess pair entropy derived from this function, plus the known perfect gas contributions, give a reasonable account of the total entropy of water, within the likely errors. This estimated entropy follows the expected declining trend with decreasing temperature. Evidence that higher density water will have higher entropy than lower density water emerges, in accordance with what is expected from the negative thermal expansion coefficient of water at low temperatures. However, this entropy increase is not large and goes through a maximum before declining at yet higher densities and pressures, in a manner reminiscent of what has been previously observed in the diffusion coefficient as a function of pressure. There is no evidence that ambient water can be regarded as patches of high density, high entropy and low density, low entropy liquid, as some have claimed, since high density water has a similar entropy to low density water. There is some evidence that the distinction between these two states will become more pronounced as the temperature is lowered. Extensive discussion of the use of order parameters to describe water structure is given, and it is pointed out that these indices generally cannot be used to infer two-state behavior.

Structure and dynamics of mesoscale eddies over the Laptev Sea continental slope in the Arctic Ocean

Abstract. Heat fluxes steered by mesoscale eddies may be a significant, but still not quantified, source of heat to the surface mixed layer and sea ice cover in the Arctic Ocean, as well as a source of nutrients for enhancing seasonal productivity in the near-surface layers. Here we use 4 years (2007–2011) of velocity and hydrography records from a moored profiler over the Laptev Sea slope and 15 months (2008–2009) of acoustic Doppler current profiler data from a nearby mooring to investigate the structure and dynamics of eddies at the continental margin of the eastern Eurasian Basin. Typical eddy scales are radii of the order of 10 km, heights of 600 m, and maximum velocities of ∼0.1 m s−1. Eddies are approximately equally divided between cyclonic and anticyclonic polarizations, contrary to prior observations from the deep basins and along the Lomonosov Ridge. Eddies are present in the mooring records about 20 %–25 % of the time, taking about 1 week to pass through the mooring at an average frequency of about one eddy per month. We found that the eddies observed are formed in two distinct regions – near Fram Strait, where the western branch of Atlantic Water (AW) enters the Arctic Ocean, and near Severnaya Zemlya, where the Fram Strait and Barents Sea branches of the AW inflow merge. These eddies, embedded in the Arctic Circumpolar Boundary Current, carry anomalous water properties along the eastern Arctic continental slope. The enhanced diapycnal mixing that we found within EB eddies suggests a potentially important role for eddies in the vertical redistribution of heat in the Arctic Ocean interior.

Interstitial Voids and Resultant Density of Liquid Water: A First-Principles Molecular Dynamics Study.

Many anomalous properties of water can be explained on the basis of the coexistence of more than one density states: high-density water (HDW) and low-density water (LDW). We investigated these two phases of water molecules through first-principles molecular dynamics simulations using density functional theory (DFT) in conjunction with various van der Waals-corrected exchange and correlation functionals. Different density regions were found to exist due to the difference in short-range and long-range forces present in DFT potentials. These density regions were identified and analyzed on the basis of the distribution of molecules and voids present. We defined a local structure index to distinguish and find the probability of occurrence of these different states. HDW and LDW arise due to the presence of “interstitial water” molecules in between the first and second coordination shells. The population of interstitial water molecules is found to affect the overall dynamics of the system as they change the hydrogen bond pattern.

Chemical physics of water

There is hardly any aspect of our lives that is not profoundly influenced by water. From climate to commerce and agriculture to health, water shapes our physical environment, regulates the major energy exchanges that determine climate on Earth, and is the matrix that supports the physical and chemical processes of life as we know it (1). The chemistry and physics of water, which underlie all of its uses, its necessity for life, its effects on other molecules and on the environment, are very active areas of research at the present time. So, why is this? Surprisingly, there are major gaps in knowledge and understanding that persist despite this substance’s ubiquity and central importance. This Special Feature on the Chemical Physics of Water contains 10 articles and aims to be a representative cross-section of current frontier research in this field. Articles include both Perspectives and original research contributions. The pioneering paper by Bernal and Fowler dealing with the chemical physics of water appeared in 1933 (2). It focused on understanding the anomalous properties of water and its ionic solutions from a molecular perspective, inspired by the newly minted quantum mechanical theory of electronic structure. Since that time, theory and computer simulation have become established as essential complements to laboratory experiments in unraveling the crucial role of water in an array … [↵][1]1To whom correspondence may be addressed. Email: pdebene{at}princeton.edu or mike.klein{at}temple.edu. [1]: #xref-corresp-1-1

Berezinskii–Kosterlitz–Thouless transition and two-dimensional melting**This review is an extended version of the report “Old and new in the physics of phase transitions” presented at the scientific session of the Physical Sciences Division of the Russian Academy of Sciences on 21 December 2016 (see Phys. Usp. 60 948–957 (2017); Usp. Fiz. Nauk 187 1021 (2017)). (Editor’s note.)

The main aspects of the theory of phase transitions in two-dimensional degenerate systems (Berezinskii–Kosterlitz–Thouless, or BKT, transitions) are reviewed in detail, including the transition mechanism, the renormalization group as a tool for describing the transition, and how the transition scenario can possibly depend on the core energy of topological defects (in particular, in thin superconducting films). Various melting scenarios in two-dimensional systems are analyzed, and the current status of actual experiments and computer simulations in the field is examined. Whereas in three dimensions melting always occurs as a single first-order transition, in two dimensions, as shown by Halperin, Nelson, and Young, melting via two continuous BKT transitions with an intermediate hexatic phase characterized by quasi-long-range orientational order is possible. But there is also a possibility for a first-order phase transition to occur. Recently, one further melting scenario, different from that occurring in the Berezinskii–Kosterlitz–Thouless–Halperin–Nelson–Young theory, has been proposed, according to which a solid can melt in two stages: a continuous BKT-type solid–hexatic transition and then a first-order hexatic-phase–isotropic-liquid phase transition. Particular attention is given to the melting scenario as a function of the potential shape and to the random pinning effect on two-dimensional melting. In particular, it is shown that random pinning can alter the melting scenario fundamentally in the case of a first-order transition. Also considered is the melting of systems with potentials having a negative curvature in the repulsion region–potentials that are successfully used in describing the anomalous properties of water in two dimensions.