Tetrahedral Order Parameter Research Articles

Dynamics of confined water inside carbon nanotubes based on studying tetrahedral order parameters

Water dynamics inside hydrophobic confinement, such as carbon nanotubes (CNTs), has garnered significant attention, focusing on water diffusion. However, a crucial aspect remains unexplored - the influence of confinement size on water ordering and intrinsic hydrogen bond dynamics. To address this gap, we conducted extensive molecular dynamics simulations to investigate local ordering and intrinsic hydrogen bond dynamics of water molecules within CNTs of various sizes (length:20 nm, diameters: 1.0 nm to 5.0 nm) over a wide range of temperatures (260K, 280K, 300K, and 320K). A striking observation emerged: in smaller CNTs, water molecules adopt an icy structure near tube walls while maintaining liquid state towards the center. Notably, water behavior within a 2.0 nm CNT stands out as an anomaly, distinct from other CNT sizes considered in this study. This anomaly was explained through the formation of water layers inside CNTs. The hydrogen bond correlation function of water within CNTs decayed more slowly than bulk water, with an increasing rate as CNT diameter increased. In smaller CNTs, water molecules hold onto their hydrogen bond longer than larger ones. Interestingly, in larger CNTs, the innermost layer’s hydrogen bond lasts a shorter time compared to the other layers, and this changes with temperature.

A Molecular Dynamics Analysis of the Thickness and Adhesion Characteristics of the Quasi-Liquid Layer at the Asphalt-Ice Interface.

The quasi-liquid layer (QLL), a microstructure located between ice and an adhering substrate, is critical in generating capillary pressure, which in turn influences ice adhesion behavior. This study employed molecular dynamics (MD) methods to obtain QLL thickness and utilized these measurements to estimate the adhesive strength between ice and asphalt. The research involved constructing an ice-QLL-asphalt MD model, encompassing four asphalt types and five temperature ranges from 250 K to 270 K. The QLL thickness was determined for various asphalts and temperatures using the tetrahedral order parameter gradient. Additionally, capillary pressure was calculated based on the QLL thickness and other geometric parameters obtained from the MD analysis. These findings were then compared with ice adhesion strength data acquired from pull-off tests. The results indicate that QLL thickness varies with different asphalt types and increases with temperature. At a constant temperature, the QLL thickness decreases in the order of the basal plane, primary prism plane, and secondary prism plane. Furthermore, the adhesion strength of the QLL diminishes as the temperature rises, attributed to the disruption of hydrogen bonds at lower temperatures. The greater the polarity of the asphalt's interface molecules, the stronger the adhesion strength and binding free energy. The MD simulations of the asphalt-ice interface offer insights into the atomic-scale adhesive properties of this interface, contributing to the enhancement in QLL property prediction and calibration at larger scales.

A close look at the hydration layer and at the premelting layer of K-feldspar

In this work, we perform molecular dynamics simulations to investigate the structural properties of water at the interface with K-feldspar. We aim at understanding the modifications induced on water structure by the presence of this mineral. We analysed both the hydration layer of K-feldspar in supercooled water and the premelting layer at the interface between K-feldspar and hexagonal ice. We studied the density profile, the orientational tetrahedral order parameter, the distribution of the cos ⁡ ( γ ) function, the hydrogen bond distribution, the number of water molecules belonging to different phases close to the surface of the feldspar. We focused on the interplay between high-density water and low-density water to inquire on local modifications of water structure with respect to the bulk phase. We investigated four different pressures where the structure of bulk water spans from high-density liquid (locally more disordered) to low-density liquid (locally more ordered). The investigation showed that both the hydration and the premelting layers present a low-density liquid water component and similarities as a function of pressure with the corresponding bulk. We also find that the premelting layer shows structural features intermediate between the liquid and the crystalline state acting as a matching layer.

Uniqueness of Nanoscale Confinement for Fast Water Transport: Effect of Nanotube Diameter and Hydrophobicity.

Inspired by the enhanced water permeability of carbon nanotubes (CNTs), molecular dynamics simulations were performed to investigate the transport behavior through nanotubes made of boron nitride (BNNT), silicon carbide (SiC), and silicon nitride (SiN) alongside carbon nanotubes (which have different hydrophobic attributes) considering their implication for reverse osmosis (RO) membranes under different practical environments. According to our findings, not only do CNTs but also other kinds of nanotubes exhibit transition anomalies with increasing diameter. Utilizing the robust two-phase thermodynamic (2PT) methods, the current examinations shed light on thermodynamic origin of favorable water filling of these nanotubes. The results show that regardless of the nanotube material, the filling of water inside small nanopores (d < 10 Å) as well as within pores of diameter larger than 15 Å will always be favored by the entropy of filling. However, the entropic preference for filling nanotubes with a diameter of 10-15 Å depends on the constituent material. In particular, the enhancement in total entropy of confined water was mainly due to the increased rotational freedom of confined water molecules. The thermodynamic origin of water transport was correlated with the structural and fluidic behavior of water inside these nanotubes. The observed data for density, flow, structure correlation functions, water-water coordination, tetrahedral order parameter, hydrogen bonds, and density of states functions quantitatively support the observed entropy behavior. Of critical importance is that the present study demonstrates the effectiveness of RO filtration using nanotubes of boron nitride rather than carbon. Furthermore, it was found that one should avoid the use of silicon nanotubes unless filtration needs to be performed under harsh environments where nanotube of other materials cannot survive. Specifically, the results show that both the structural and dynamic properties of water confined in BNNTs are similar to those of CNT's, and for SiNT it is similar as SiC. Our results show that besides the nanotube material, the chirality index of the nanotube also plays a significant role in determining the structure, dynamics and thermodynamics of confined water molecules.

Impact and structure of water in aqueous octanol mixtures: Hz-GHz dielectric relaxation measurements and computer simulations

Temperature (283 ≤ T/K ≤ 323) dependent dielectric relaxation (DR) measurements of aqueous binary mixtures of octanol at three different water mole fractions (XH2O = 0.05, 0.10, 0.20) were performed employing two different frequency windows: 0.00002 ≤ν/MHz≤ 10 and 0.2 ≤ν/GHz≤ 50. In addition, DR measurements were carried out for pure octanol and water saturated octanol at 298 K. All these measurements showed, irrespective of solution temperature, a small decrease of the static dielectric constant (εs) upon addition of water in octanol. Two-step relaxation process with time constants ∼ 3–0.3 ns and ∼ 120–40 ps characterized the measured DR spectra with no signature of bulk water-like DR time constant (∼10 ps). Differential scanning calorimetric (DSC) measurements of octanol + water mixtures reflect only water concentration dependent depression of octanol freezing temperature. Our computer simulations of aqueous octanol mixtures with SPC/E water suggests a dramatic decrease of the average number of water-water H-bonds 〈NHBw-w〉 per water molecule and a spectacular increase of water populations possessing OOO angles distributed over 0°≤θ≤ 60°. Consequently, a negative value for the average tetrahedral order parameter (〈Q〉) and an εs as low as ∼ 2 for water have been predicted. A severe damage to the global tetrahedrality of water in these mixtures has been predicted and the angle distributions corresponding to negative and positive Q values explicitly shown. These simulation results therefore explain the microscopic origin for small effects of water at low mole fractions on εs of octanol + water binary mixtures.

Anisotropy and Hybrid Heterosurface-Modulated Two-Dimensional Hydrogen Bond Network of Water

We report the structure and dynamics of layered water structure near a bilayer heterosurface using classical molecular dynamics simulations and network graph theory. The heterosurfaces of our choice are technologically essential and well-studied hexagonal boron nitride (h-BN) and graphitic carbon nitride (g-C3N4). Starting with the water density distribution profile, we have studied different hydrogen bondings (HBs) associated with distance and angle distributions and correlated them with the HB count, followed by the investigations of dynamic properties. We realize the oddity while corresponding to the tetrahedral order parameter (TOP), HB donor/acceptor count, and HB lifetime. A quantitative gap is observed between the TOP and HB counts, and we perceive another structural factor playing a significant role. We observe a 2D sheetlike arrangement of hydrogen-bonded water molecules, namely, 2D-HB, in the interfacial layer instead of 3D tetrahedral arrangements. 2D-HB qualitatively acts as a key descriptor of the hydrophobicity of the interface. The probability of higher TOP among the interfacial layer water molecules is less for h-BN compared to g-C3N4. However, the per-water HBs for both the heterosurfaces remain indistinguishable, implying the existence of another significant physical factor related to HB. Hence, 2D-HB serves as a deciding factor. In the case of h-BN, water molecules in the first layer form extended 2D sheets compared to the second and bulk, which is not a scenario for g-C3N4. Following the network graph theory, we calculated the temporal evolution of the maximum number of water molecules connected in a single network. The layer 1 water molecules have slower orientational dynamics, higher HB lifetime, and consequently slower translational diffusion than layer 2 and bulk water molecules. The experimental studies suggested that the contact angle of water on h-BN can vary from 61.4 to 85.8°, higher than that of g-C3N4, depending on the surface stacking, support material, and exposure to air, which effectively makes h-BN more hydrophobic compared to g-C3N4. The interfacial water molecules have a smaller HB lifetime and a faster diffusion coefficient than g-C3N4. The HB lifetime of water molecules in bulk is less than that in the interface, irrespective of the surface. A slower reorientation lifetime, that is, 2.69 ps, for g-C3N4 interfacial water molecules is observed versus 2.20 ps for h-BN. Our results agree with the experimental observations and can help to understand the hydrophobicity of other relevant materials.

Topology-Based Phase Identification of Bulk, Interface, and Confined Water Using an Edge-Conditioned Convolutional Graph Neural Network

Water plays a significant role in various physicochemical and biological processes. Understanding and identifying water phases in various systems such as bulk, interface, and confined water is crucial in improving and engineering state-of-the-art nanodevices. Various order parameters have been developed to distinguish water phases, including bond-order parameters, local structure index, and tetrahedral order parameters. These order parameters are often developed with the assumption of homogenous bulk systems, while most applications involve heterogeneous and non-bulk systems, thus limiting their generalizability. Our study develops a methodology based on a graph neural network to distinguish water phases directly from data and to learn features instead of predefining them. We provide comparisons between baseline methods trained using conventional order parameters as features and a graph neural network model trained using radial distance and hydrogen-bonding information to study phase classification and continuous and discontinuous phase transitions of bulk, interface, and confined water.

Protein hydration water: Focus on low density and high density local structures upon cooling

We report results about the structure of protein hydration water upon cooling compared to bulk water. We focus on the analysis of the local structure through order parameters: the tetrahedral order parameter q and a recently introduced parameter V4. Both parameters show that, similarly to bulk water, protein hydration water is a mixture of two liquids already at ambient conditions. These liquids are a low density liquid (LDL) characterized by a more tetrahedral-ordered local structure and a high density liquid (HDL) that is more distorted. Protein hydration water has a higher concentration of HDL with respect to LDL if compared to the bulk case upon cooling. The two water populations of hydration water are also less sensitive to temperature variations with respect to bulk water. The presence of the protein affects the structure of hydration water that is locally more distorted than bulk water. Both the parameters display a two-liquid picture of hydration water. Correlations between the two parameters are also investigated. In spite of the differences found in hydration water with respect to the bulk the bimodal structure is importantly preserved.

Dynamical Anomaly of Aqueous Amphiphilic Solutions: Connection to Solution H-Bond Fluctuation Dynamics?

We have investigated the possible connection between “dynamical anomaly” observed in time-resolved fluorescence measurements of reactive and nonreactive solute-centered relaxation dynamics in aqueous binary mixtures of different amphiphiles and the solution intra- and interspecies H-bond fluctuation dynamics. Earlier studies have connected the anomalous thermodynamic properties of binary mixtures at very low amphiphile concentrations to the structural distortion of water. This is termed as “structural anomaly.” Interestingly, the abrupt changes in the composition-dependent average rates of solute relaxation dynamics occur at amphiphile mole fractions approximately twice as large as those where structural anomalies appear. We have investigated this anomalous solution dynamical aspect by considering (water + tertiary butanol) as a model system and performed molecular dynamics simulations at several tertiary butanol (TBA) concentrations covering the extremely dilute to the moderately concentrated regimes. The “dynamical anomaly” has been followed via monitoring the composition dependence of the intra- and interspecies H-bond fluctuations and reorientational relaxations of TBA and water molecules. Solution structural aspects have been followed via examining the tetrahedral order parameter, radial and spatial distribution functions, numbers of H bonds per water and TBA molecules, and the respective populations participating in H-bond formation. Our simulations reveal abrupt changes in the H-bond fluctuations and reorientational dynamics and tetrahedral order parameter at amphiphile concentrations differing approximately by a factor of 2 and corroborates well with the steady-state and the time-resolved spectroscopic measurements. This work therefore explains, following a uniform and cogent manner, both the experimentally observed structural and dynamical anomalies in microscopic terms.

How Far Is "Bulk Water" from Interfaces? Depends on the Nature of the Surface and What We Measure.

Using systematic molecular dynamics (MD) simulations, we revisit the question: At what distance from an interface do the properties of "bulk water" get recovered? We have considered three different kinds of interfaces: nonpolar (hydrophobic; isooctane-water interface), charged (negative; AOT bilayer), and polar (zwitterionic; POPC bilayer). In order to interrogate the extent of perturbation of the interfacial water molecules as a function of the distance from the interface, we utilize a diverse range of structural and dynamical parameters. To capture the structural perturbations, we look into local density (translational order), local tetrahedral order parameter, and dipolar orientation of the water molecules. We also explore the anisotropic diffusion of the water molecules in the direction perpendicular to the interface as well as the planar diffusion parallel to the interface in a distance dependent manner. In addition, the orientational time correlation functions have been computed to understand the extent of slowdown in the rotational dynamics. As expected, the electrostatic field emanating from the charged AOT interface seems to have the highest long-range effect on the orientational order and dynamics of the water molecules, whereas specific interactions like hydrogen bonding and electrostatic interaction lead to significant trapping and kinetic slowdown for both AOT and POPC (zwitterionic) very close to the interface. Our analysis highlights that not only the length-scale of perturbation depends on the nature of the interfaces and specific interactions but also the type of water property that we measure/calculate. Different water properties seem to have widely different length-scale of perturbation. Orientational order parameters seem to be perturbed to a much longer length-scale as compared to translational order parameters. The global orientational order of water can be perturbed even up to ∼4-5 nm near the negatively charged AOT surface in the absence of any extra electrolyte. This observation has significant implication toward the interpretation of experimental measurements as well since different spectroscopic techniques would probe different parameters or water properties with possible mutual disagreement and inconsistency between different types of measurements. Thus, our study provides a broader and unifying perspective toward the aspect of "context dependent" structural and dynamical perturbation of "interfacial water".

Size-Dependent Order-Disorder Crossover in Hydrophobic Hydration: Comparison between Spherical Solutes and Linear Alcohols.

Theory and computer simulation studies have predicted that water molecules around hydrophobic molecules should undergo an order–disorder transition with increasing solute size around a 1 nm length scale. Some theories predict the formation of a clathrate-like ordered structure around smaller hydrophobic solutes (<1 nm) and the formation of disordered vapor–liquid interfaces around larger solutes (>1 nm) and surfaces. Experimental validation of these predictions has often been elusive and contradictory. High-resolution Raman spectroscopy has detected that water around small hydrophobic solutes shows a signature similar to that of bulk water at lower temperature (increased ordering and a stronger hydrogen-bonded network). Similarly, water around larger solutes shows an increasing population of dangling OH bonds very similar to higher temperature bulk water. Thus, the solute size dependence of the structure and dynamics of water around hydrophobic molecules seems to have an analogy with the temperature dependence in bulk water. In this work, using atomistic classical molecular dynamics (MD) simulations, we have systematically investigated this aspect and characterized this interesting analogy. Structural order parameters including the tetrahedral order parameter (Q), hydrogen bond distribution, and vibrational power spectrum highlight this similarity. However, in contrast to the experimental observations, we do not observe any length-dependent crossover for linear hydrophobic alcohols (n-alkanols) using classical MD simulations. This is in agreement with earlier findings that linear alkane chains do not demonstrate the length-dependent order–disorder transition due to the presence of a sub-nanometer length scale along the cross section of the chain. Moreover, the collapsed state of linear hydrocarbon chains is not significantly populated for smaller chains (number of carbons below 20). In the context of our computational results, we raise several pertinent questions related to the sensitivity of various structural and dynamical parameters toward capturing these complex phenomena of hydrophobic hydration.

Solvation of gold nanoparticles passivated with functionalized alkylthiols: A molecular dynamics study

Molecular dynamics simulations of gold nanoparticles (NPs) passivated with end-group functionalized alkylthiols, namely CH3, NH2, or COOH in solvents of varying degrees of repulsion-dispersion and electrostatic interactions ranging from strongly polar SPC/E water to modified hybrid water models (H1.56 and H3.00), where the Lennard-Jones contribution to the potential energy is enhanced relative to SPC/E to completely non-polar, decane, are performed. The effects due to solvent reorganization around the NP as a function of the ligand and solvent chemistry are monitored using the NP-solvent pair correlation functions and tetrahedral order parameter. The solvent penetration inside the ligand shell is maximum for decane, indicating better solute–solvent interaction in decane as compared to other solvents. The COOH end-group functionalized NP is observed to break the tetrahedral structure of water molecules more as compared to other NPs used in this study. Radial density profiles and radius of gyration values show significant stretching of the ligands in decane than in the model waters, which is also consistent with the ligand asymmetry parameter. The ligand shell anisotropy for all NPs is maximum in SPC/E water and minimum in decane. The isotropic potential of mean force between two identical end-group functionalized NPs show attractive well depth in vacuum, SPC/E water, and H3.00 modified hybrid water. The implications for self-assembly of passivated gold NPs from aqueous dispersions as well as the dependence of calculated quantities on ligand and solvent chemistry are highlighted.

Structure and rotational dynamics of water around hydrogen peroxide

The density functional theory-based molecular dynamics simulations were induced to study various properties of water around different solvation pockets around hydrogen peroxide(H2O2). Our study aims to understand water behavior in the vicinity of H2O2 molecule through analyzing structure, hydrogen bond statistics, orientational and non-diffusive jump profile. A water-like peroxide molecule can form four hydrogen bonds with nearby water molecules: two as a proton donor and two as a proton acceptor, which must disturb the local structure and dynamics of the surrounding water. The presence of two different peak maxima in radial distribution function (RDF) allows us to resolve the solvation environment into three solvation sites: solvation shell I, solvation shell II, and bulk. The probability distribution of the average distance of central water molecule from 4 nearest water molecules shows a shift in the peak for solvation shell I water molecules towards a ∼0.3Å higher value compared to two other solvation shells. This further affects tetrahedral order parameters as water molecules shift from the regular tetrahedron. For the first solvation layer, the water molecules lose their tetrahedrality to a significant extent as qtet probability distribution peaks at 0.5 and broaden in the higher values of qtet without any shoulder. For the second solvation layer, we find the qtet peak at 0.87 with a minor shoulder appearing at qtet = 0.55, a sign of slight loss of tetrahedrality in the unstructured water compared to undisturbed water. Loss of tetrahedrality hints at the change of orientation of H2O molecules in the vicinity of H2O2 and affects the water-water hydrogen bond (HB) formation. A noteworthy reduction in the HB donor/acceptor account and per water HB count shows interference of H2O2. The water molecules prefer H2O2 compared to neighboring water molecules for HB formation. The orientation autocorrelation function provides the rotational pace of water molecules in the different solvation layers. The reorientation time constant difference in the solvation shells I and II fluctuate by mere 0.20 ps, showcasing the trivial nature of hydrogen peroxide and water HBs. Using the HB descriptors, we also report the non-diffusive jump profile involving vicinal water molecules of H2O2. The jump angle profile of solvation shell water molecules is in line with bulk water.

Amphiphilicity of Intricate Layered Graphene/g-C3N4 Nanosheets.

The hybrid heterostructure of the tri-s-triazine form of graphitic carbon nitride (g-C3N4), a stable two-dimensional material, results from intricate layer formation with graphene. In this material, g-C3N4, an amphiphilic material, stabilizes Pickering emulsions as an emulsifier and can effectively disperse graphene. Due to the various technological applications of the hybrid nanosheets in an aqueous environment, it is essential to study the interaction of water molecules with graphene and g-C3N4 (Gr/g-C3N4)-combined heterostructure. Although few studies have been performed signifying the water orientation in the interfacial layer, we find that there is a lack of detailed studies using various dynamical and structural properties of the interfacial water molecules. The interface of the Gr/g-C3N4 hybrid structure, one of the rarely found amphiphilic interfaces (on the g-C3N3 side), is appropriate for exploring the water affinity due to the availability of heterogeneous interfacial aqueous interactions. We adopted classical molecular dynamics simulations using two models for water molecules to study the structure and dynamics of an aqueous interface. We have correlated the structural properties to dynamics and spectral properties to understand the overall behavior of the amphiphilic interface. Our results branch into two significant hydrogen bond (HB) properties in HB count and HB strength among the water molecules in the different layers. The HB counts in the different layers of water are correlated using the average distance distribution (PrO4), tetrahedral order parameters, HB donor/acceptor count, and total HBs per water molecule. A conspicuous difference is found in the HB count and related dynamics of the system. The HB lifetime and diffusion coefficient hint at the equivalent strength of HBs in the different layers. All the findings conclude that the amphiphilicity of the Gr/g-C3N4 interface can help in understanding various interfacial physical and chemical processes.

Preferential binding affinity of ions and their effect on structure and dynamics of water near antimicrobial peptide

Water containing dissolved salts is often found to play important roles in many chemical and biological processes. They affect the stability of the amino acids and proteins by altering the liquid water structure. The formation of a mixture of non-uniform density regions in liquid water; commonly known as Low-density water and High-density water is a well-known fact experimentally; which lends uniqueness to the ubiquitous water. The behavior of these different types of water at the interface and the bulk region of the biomolecules around the hydrophobic and hydrophilic residues under the influence of different alkali metal ions, such as LiCl, NaCl, and KCl is an important unexplored question in understanding of many biomolecular processes. To address this, we carried out MD simulation of antimicrobial peptide (PDB ID: 5Z32) for two different model potentials (CHARMM-SPC/E and AMBER-TIP4P) and performed the structural analysis of water in terms of the radial distribution function, number of hydrogen bonds, orientation, tetrahedral order parameter, voids analysis to analyze the related dynamical properties like preferential binding affinity, diffusion, hydrogen bond dynamics, entropy. The water molecules around the hydrophilic environment are found to be more disruptive containing more broken hydrogen bonds in comparison to the hydrophobic environment. It is also found that the water molecules present near the protein surface are of low density and that near the bulk is of high density. This leads to the higher self-diffusion coefficient of the water molecules and less hydrogen bond lifetime at the bulk. The maximum difference is found for the solutions containing high charge density, Lithium ions. Lithium ions have a strong preferential binding affinity towards protein surface resulting in strong solvation shells containing more tetrahedral-like water structure which has low diffusion, low entropy, and higher hydrogen bond lifetime. The diffusion of the water molecules, however, increases towards the higher solvation shells. Potassium on the other hand has less preference to live on protein surfaces resulting in similar diffusion values in the bulk and interface water molecules.

Effects of interfaces on structure and dynamics of water droplets on a graphene surface: A molecular dynamics study

The structure and dynamics of water droplets on a bilayer graphene surface are investigated using molecular dynamics simulations. The effects of solid/water and air/water interfaces on the local structure of water droplets are analyzed in terms of the hydrogen bond distribution and tetrahedral order parameter. It is found that the local structure in the core region of a water droplet is similar to that in liquid water. On the other hand, the local structure of water molecules at the solid/water and air/water interfaces, referred to as the interface and surface regions, respectively, consists mainly of three-coordinated molecules that are greatly distorted from a tetrahedral structure. This study reveals that the dynamics in different regions of the water droplets affects the intermolecular vibrational density of states: It is found that in the surface and interface regions, the intensity of vibrational density of states at ∼50 cm-1 is enhanced, whereas those at ∼200 and ∼500 cm-1 are weakened and redshifted. These changes are attributed to the increase in the number of molecules having fewer hydrogen bonds in the interface and surface regions. Both single-molecule and collective orientation relaxations are also examined. Single-molecule orientation relaxation is found to be marginally slower than that in liquid water. On the other hand, the collective orientation relaxation of water droplets is found to be significantly faster than that of liquid water because of the destructive correlation of dipole moments in the droplets. The negative correlation between distinct dipole moments also yields a blueshifted libration peak in the absorption spectrum. It is also found that the water-graphene interaction affects the structure and dynamics of the water droplets, such as the local water structure, collective orientation relaxation, and the correlation between dipole moments. This study reveals that the water/solid and water/air interfaces strongly affect the structure and intermolecular dynamics of water droplets and suggests that the intermolecular dynamics, such as energy relaxation dynamics, in other systems with interfaces are different from those in liquid water.

Insignificant Effect of Temperature on the Structure and Angular Jumps of Water near a Hydrophobic Cation.

The ambiguity in the behavior of water molecules around hydrophobic solutes is a matter of interest for many studies. Motivated by the earlier results on the dynamics of water molecules around tetramethylammonium (TMA) cation, we present the effect of temperature on the structure and angular jumps of water due to hydrophobicity using first principles molecular dynamics simulations. The average intermolecular distance between the central oxygen and four nearest neighbors is found to be the highest for water molecules in the solvation shell of TMA at 400 K, followed by the same at 330 K. The hydrogen bond (HB) donor–acceptor count, HB per water molecule, and tetrahedral order parameter suggests the loss of tetrahedrality in the solvation shell. Elevated temperature affects the tetrahedral parameter in local regions. The HB jump mechanism is studied for methyl hydrogen and water molecules in the solvation shell. Observations hint at the presence of dangling water molecules in the vicinity of the hydrophobic cation, and no evidence is found for the enhanced structural ordering of nearby water molecules.

Molecular dynamics simulation of thermal de-icing on a flat surface

The accumulation of ice has adverse effects on human activities but the dynamic mechanism of icing and de-icing has not been well clarified. Herein, molecular dynamics (MD) simulations and the analysis methods of the hydrogen bond and the tetrahedral order parameter are used for the first time to investigate the underpinning physics and visualize the thermal de-icing process on a flat wall from the molecular level. The effects of ice thickness (H), wall temperature (Tw) and wettability on the thermal de-icing process are examined. The results indicate that the ice starts to melt from its mantle and then proceeds inwards. The energy consumption of thermal de-icing can be modelled as a bilinear function of Tw and H. The melting time is almost bilinear with respect to H and 1/(Tw-273.15K), and converges to a constant value at Tw⩾313.15K. When adopting a hydrophobic surface, which is generally considered as icephobic and prevents the ice accretion, more time and almost constant energy are required to melt the ice. By revealing thermal de-icing processes on a hot surface at the molecule level, this work offers guidance for the development of de-icing techniques and devices applied extensively in engineering applications.

Structural (dis)order and dynamic propensity in a mildly undercooled glass-forming liquid: Spatial correlations and the role of crystalline environments

We use the isoconfigurational (IC) ensemble to show the connection between emerging heterogeneities in the tetrahedral order parameter and the dynamic propensity in a mildly undercooled glass-forming liquid. We observe that spatially correlated tetrahedrally-(dis)ordered clusters of molecules are observable on the time scale of structural relaxation. The heterogeneities of tetrahedrally-(dis)ordered clusters correlate with dynamical heterogeneities (DH) and these correlations reach peaks at similar time scales. We discover that the angular component of the tetrahedral order parameter is strongly correlated to the dynamics compared to the radial component. Moreover, these correlations between the dynamics and tetrahedrally-(dis)ordered regions enormously influence the system, with spatial correlations being observable for a prolonged period beyond the peaks of maximum DH. Further, we discover that the crystalline particle environments in our water model (as identified by the IC ensemble) may be the origin for slow dynamics of dynamical heterogeneity in our undercooled model water system.

Structure and thermodynamics of empty clathrate hydrates below the freezing point of water.

Recently prepared as a new H2O phase, ice XVI was obtained by degassing a Ne-sII clathrate hydrate under vacuum, however very little is known of that crystalline solid under temperatures (T ≤ 220 K) and pressures (p ≤ 5000 bar) relevant for the Earth's environment and geochemistry. In this work, atomically detailed calculations using long time-scale molecular simulations, seldom paralelled before, are employed to probe empty sII clathrate hydrates. It is found that the volumetric response to an applied pressure-temperature gradient is accurately described by the Parsafar and Mason equation of state with an accuracy of at least 99.7%. Structural deformation induced upon the crystals is interpreted by monitoring the unit cell length and isobaric thermal expansivity, whilst benchmarked against previous neutron diffraction measurements of ice XVI and hexagonal ice under room pressure conditions; a critical comparison is established with other sII guest occupied lattices (CH4, CO2 and CnH2n+2 with n = 2, 3, 4), often found in permafrost regions and in the margins of continental shelves. Such an analysis reveals that empty sII frameworks are slightly more stable to thermal deformation than their sI analogues and that hexagonal ice is the structurally most stable of the condensed H2O phases addressed here. Of paramount importance for the oil and natural gas industries, heat capacities obtained from enthalpy profiles are identical for the sI and sII empty clathrates up to 2000 bar and diverge by only ∼7.3% at 5000 bar. The canonical tetrahedral symmetry of water-bonded networks is analysed in terms of an angular and a distance order parameters, which are observed to decrease (increase) as pressure (temperature) increases (decreases). The results now being reported constitute a landmark for future studies dealing with high-pressure and very low-temperature conditions, characteristic of the Earth's permafrost environment and other planetary interiors, whilst contributing to expand our knowledge regarding the recently discovered ice XVI phase.