Water Clusters Research Articles

DISCUSSION OF THE MECHANISM OF THE ELECTRICAL CONDUCTIVITY OF PURE WATER IN THE FRAMEWORK OF THE BJERRUM MODEL

An alternative mechanism of electrical conductivity and ionization of molecules in pure water is considered. Calculation of the temperature dependence for the activation energy of ionization of water molecules was carried out using data on the value of its ionic product. The calculated activation energies for the ionization and flow processes show the presence of a certain proportionality between them. This suggests that the ionization of water is caused by intermolecular forces rather than intramolecular forces. Accordingly, the electrical conductivity of water is associated with the appearance and movement in it of L and D defects of hydrogen bonds between water molecules, which have significant electrical pseudo charges and are considered in the Bjerrum model for ice. This work proposes a new interpretation of the mechanism of ionization (pseudoionization) of molecules and generation of L and D defects in water. Rotation is considered not for one, but for two of its molecules in opposite directions with partial compensation of their angular momentum, and the breaking of not three bonds for one molecule, but four bonds with neighbors for two molecules. Moreover, these four neighbors do not include molecules from water clusters that have stronger bonds, since neighboring molecules with weaker bonds can be found for the process of rotation activation. Accordingly, the exponential contribution made by molecules from water clusters is absent or small in the ionization activation energy. In this way, the activation energy for the flow, which occurs throughout the entire volume of the liquid and automatically includes molecules from clusters, differs from the activation energy of electrical conductivity, which occurs for individual molecules in chains of bonds. The presence of a maximum in the ionic product of water near 250 ⁰C can be explained by the rapid decrease in the lifetime of L and D defects with heating, which prevents the use of the standard equation for accurate calculation of the ionization activation energy above 100...200 ⁰C. However, the presence of this maximum contradicts the generally accepted model of proton hopping between neighboring hydronium and water molecules in the mechanism of its electrical conductivity.

Flat-Histogram Monte Carlo Simulation of Water Adsorption in Metal-Organic Frameworks.

Molecular simulations of water adsorption in porous materials often converge slowly due to sampling bottlenecks that follow from hydrogen bonding and, in many cases, the formation of water clusters. These effects may be exacerbated in metal-organic framework (MOF) adsorbents, due to the presence of pore spaces (cages) that promote the formation of discrete-size clusters and hydrophobic effects (if present), among other reasons. In Grand Canonical Monte Carlo (MC) simulations, these sampling challenges are typically manifested by low MC acceptance ratios, a tendency for the simulation to become stuck in a particular loading state (i.e., macrostates), and the persistence of specific clusters for long periods of the simulation. We present simulation strategies to address these sampling challenges, by applying flat-histogram MC (FHMC) methods and specialized MC move types to simulations of water adsorption. FHMC, in both Transition-matrix and Wang-Landau forms, drives the simulation to sample relevant macrostates by incorporating weights that are self-consistently adjusted throughout the simulation and generate the macrostate probability distribution (MPD). Specialized MC moves, based on aggregation-volume bias and configurational bias methods, separately address low acceptance ratios for basic MC trial moves and specifically target water molecules in clusters; in turn, the specialized MC moves improve the efficiency of generating new configurations which is ultimately reflected in improved statistics collected by FHMC. The combined strategies are applied to study the adsorption of water in CuBTC and ZIF-8 at 300 K, through examination of the MPD and the adsorption isotherm generated by histogram reweighting. A key result is the appearance of nontrivial oscillations in the MPD, which we show to be associated with water clusters in the adsorption system. Additionally, we show that the probabilities of certain clusters become similar in value near the boundaries of the isotherm hysteresis loop, indicating a strong connection between cluster formation/destruction and the thermodynamic limits of stability. For a hydrophobic MOF, the FHMC results show that the phase transition from low density to high density is suppressed to water pressure far above the bulk-fluid saturation pressure; this is consistent with results presented elsewhere. We also compare our FHMC simulation isotherm to one measured by a different technique but with ostensibly the same molecular interactions and comment on observed differences and the need for follow-up work. The simulation strategies presented here can be applied to the simulation of water in other MOFs using heuristic guidelines laid out in our text, which should facilitate the more consistent and efficient simulation of water adsorption in porous materials in future applications.

Photomolecular effect: Visible light interaction with air–water interface

Although water is almost transparent to visible light, we demonstrate that the air-water interface interacts strongly with visible light via what we hypothesize as the photomolecular effect. In this effect, transverse-magnetic polarized photons cleave off water clusters from the air-water interface. We use 14 different experiments to demonstrate the existence of this effect and its dependence on the wavelength, incident angle, and polarization of visible light. We further demonstrate that visible light heats up thin fogs, suggesting that this process can impact weather, climate, and the earth's water cycle and that it provides a mechanism to resolve the long-standing puzzle of larger measured clouds absorption to solar radiation than theory could predict based on bulk water optical constants. Our study suggests that the photomolecular effect should happen widely in nature, from clouds to fogs, ocean to soil surfaces, and plant transpiration and can also lead to applications in energy and clean water.

Nonaggregated Anions Enable the Undercooled Aqueous Electrolyte for Low-Temperature Applications.

Aqueous batteries, with the advantages of high safety and low cost, are highly promising for large-scale energy storage. However, freezing of the aqueous electrolyte limits the low-temperature operation. Here, we propose and achieve a highly dispersed solvation structure in the electrolyte by coupling nonaggregated Cl- anions, which reduces the water cluster size and prevents the solidification of the aqueous electrolyte until -136.3 °C. The low-temperature LiCl electrolyte exhibits a high ionic conductivity (1.0 mS cm-1) at -80 °C and enables a stable low-temperature Ag/AgCl reference electrode at -50 °C. Moreover, the polyaniline-based battery can work at an extremely low temperature of -100 °C and shows superior cycling performance of 4000 cycles at -40 °C with 95.7% capacity retention. This work elucidates the correlation between the anion effect and the thermodynamic transition of the electrolyte, offering a novel approach for designing low-temperature electrolytes.

Controlling Interfacial Hydrogen Bonding at a Gold Surface: The Effect of Organic Cosolvents.

Water often serves as both a reactant and solvent in electrocatalytic reactions. Interfacial water networks can affect the transport and kinetics of these reactions, e.g., hydrogen evolution reaction and CO2 reduction reaction. Adding cosolvents that influence the hydrogen-bonding (H-bonding) environment, such as dimethyl sulfoxide (DMSO), has the potential to tune the reactivity of these important electrocatalytic reactions by regulating the interfacial local environment and water network. We investigate interfacial H-bonding networks in water-DMSO cosolvent mixtures on gold surfaces by using surface-enhanced infrared absorption spectroscopy and molecular dynamics simulations. Experiments and simulations show that the gold surface is enriched with dehydrated DMSO molecules and the mixture phase-separates to form water clusters. Simulations show a "buckled" water conformation at the surface, further constraining interfacial H-bonding. The small size of these water clusters and the energetically unfavorable H-bond conformations might inhibit H-bonding with bulk water, suppressing the proton diffusion required for efficient hydrogen evolution reaction processes.

Cell wall water induced dimensional changes of beech and pine wood

Hygroexpansion in timber construction is a phenomenon that occurs as a result of changes in the cell wall structure of wood caused by water. In this study, beech (Fagus sylvatica) and pine (Pinus taeda L.) wood were conditioned at different relative humidities with saturated salt solutions and saturated through vacuum pressure impregnation. The moisture content and dimensions of the samples were evaluated under various adsorption equilibrium states, as well as during drying from water saturation to an air-dried state. The results obtained using the two-dimensional time-domain nuclear magnetic resonance technique revealed two distinct types of cell wall water in both wood species, designated as B-water and C-water, as they displayed different mobilities. With increasing moisture content, the mobility of cell wall water increased; however, B-water maintained a constant level of mobility and formed water clusters when it accumulated in the high humidity region and at slightly above the fiber saturation point (FSP), which is evidence of the occurrence of free-bound water. The B-water, located in the amorphous region of microfibrils and their surrounding hemicellulose, exerted a predominant influence on the dimensional changes of the wood both under equilibrium and nonequilibrium conditions, in comparison to the C-water which located in the matrix of hemicellulose and lignin.

Energetics of water expulsion from intervening space between two particles during aggregation

Solvent expulsion away from an intervening region between two approaching particles plays important roles in particle aggregation yet remains poorly understood. In this work, we use metadynamics molecular simulations to study the free energy landscape of removing water molecules from gibbsite and pyrophyllite slit pores representing the confined spaces between two approaching particles. For gibbsite, removing water from the intervening region is both entropically and enthalpically unfavorable. The closer the particles approach each other, the harder it is to expel water molecules. For pyrophyllite, water expulsion is spontaneous, which is different from the gibbsite system. A smaller pore makes the water removal more favorable. When water is being drained from the intervening region, single chains of water molecules are observed in gibbsite pore, while in pyrophyllite pore water cluster is usually observed. Water-gibbsite hydrogen bonds help stabilize water chains, while water forms clusters in pyrophyllite pore to maximize the number of hydrogen bonds among themselves. This work provides the first assessment into the energetics and structure of water being drained from the intervening region between two approaching particles during oriented attachment and aggregation.

An experimental and computational view of the photoionization of diol-water clusters.

In the interstellar medium, diols and other prebiotic molecules adsorb onto icy mantles surrounding dust grains. Water in the ice may affect the reactivity and photoionization of these diols. Ethylene glycol (EG), 1,2-propylene glycol, and 1,3-propylene glycol clusters with water clusters were used as a proxy to study these interactions. The diol-water clusters were generated in a continuous supersonic molecular beam, photoionized by synchrotron-based vacuum ultraviolet light from the Advanced Light Source, and subsequently detected by reflectron time-of-flight mass spectrometry. The appearance energies for the detected clusters were determined from the mass spectra, collected at increasing photon energy. Clusters of both diol fragments and unfragmented diols with water were detected. The lowest energy geometry optimized conformers for the observed EG-water clusters and EG fragment-water clusters have been visualized using density functional theory (DFT), providing insight into hydrogen bonding networks and how these affect fragmentation and appearance energy. As the number of water molecules clustered around EG fragments (m/z 31 and 32) increased, the appearance energy for the cluster decreased, indicating a stabilization by water. This trend was supported by DFT calculations. Fragment clusters from 1,2-propylene glycol exhibited a similar trend, but with a smaller energy decrease, and no trend was observed from 1,3-propylene glycol. We discuss and suggest that the reactivity and photoionization of diols in the presence of water depend on the size of the diol, the location of the hydroxyl group, and the number of waters clustered around the diol.

Linear Scaling Incremental Scheme for Correlation Energies with Embedding Generated Virtuals.

A novel incremental scheme is presented including an incremental expansion of the virtual space for the calculation of electron correlation energies, which is compatible with any size-extensive correlation method and scales asymptotically linear for large molecules. The performance is studied for organic molecules, water clusters, and a La(III)-water complex, where the compatibility with pseudopotentials is also examined. The computational requirements are already reduced tremendously for medium-sized water clusters and hydrocarbons with respect to the canonical CCSD as well as the ordinary incremental scheme references. Correlation energies within chemical accuracy have been observed for all studied systems. The novelty of the method is that relatively small virtual spaces are used in combination with tuples of localized occupied spaces. The corresponding orthonormal occupied and virtual orbitals are obtained from QM/QM embedding calculations and can thus be used with standard quantum chemistry codes for correlation calculations. It is presented how relevant virtual spaces are selected and the correlation energies are linked in the new virtual space expansion.

Investigation on the Gas Emission Law of Water-Containing Coal across the Rank Range.

Water commonly occurs in coal reservoirs, and it can block the gas flow channels. This has a significant influence on methane transportation within coal. To reveal the gas emission law of water-containing coal across the rank range, three typical coal samples with different coal ranks covering lignite to anthracite were selected in this work. The initial velocity of gas emission (ΔP) under the effect of moisture was measured, and the combination of scanning electron microscopy and mercury injection method was adopted to study the pores and fracture characteristics within coal. Distribution features of oxygen-containing groups in coal were explored by X-ray photoelectron spectroscopy. The microscopic influence mechanism of the water content on ΔP in coal was also comprehensively elucidated. The experimental results show that the moisture content has an obvious inhibitory effect on the ΔP of coal, but the degree of influence on different coal rank samples was different. As the pore space of anthracite (sample XJ) is developed with numerous gas transportation channels, the ΔP has less changes at the lower moisture content (<4.36%). When the moisture content is >4.36%, a large number of water molecules will band together to form water clusters, hindering the gas release, thus greatly reducing the ΔP. However, the change of lignite (sample SL) shows an inverse trend to that of anthracite. Its ΔP is sensitive to the moisture content due to the small number of pores and low porosity. In addition, a great number of oxygen-containing groups in lignite can also provide good surface hydrophilicity for water molecules, and even a small amount of the moisture content (<3.21%) can block most of the pore and facture channels within coal, leading to the remarkable decrease in ΔP. For bituminous coal (sample ML), the distribution of pores and oxygen-containing groups is the most uniform, and the ΔP decreases linearly with the increase in the moisture content.

Water Arrangements upon Interaction with a Rigid Solute: Multiconfigurational Fenchone-(H2O)4-7 Hydrates.

Insight into the arrangements of water molecules around solutes is important to understand how solvation proceeds and to build reliable models to describe water-solute interactions. We report the stepwise solvation of fenchone, a biogenic ketone, with 4-7 water molecules. Multiple hydrates were observed using broadband rotational spectroscopy, and the configurations of four fenchone-(H2O)4, three fenchone-(H2O)5, two fenchone-(H2O)6, and one fenchone-(H2O)7 complexes were characterized from the analysis of their rotational spectra in combination with quantum-chemical calculations. Interactions with fenchone deeply perturb water configurations compared with the pure water tetramer and pentamer. In two fenchone-(H2O)4 complexes, the water tetramer adopts completely new arrangements, and in fenchone-(H2O)5, the water pentamer is no longer close to being planar. The water hexamer interacts with fenchone as the least abundant book isomer, while the water heptamer adopts a distorted prism structure, which forms a water cube when including the fenchone oxygen in the hydrogen bonding network. Differences in hydrogen bonding networks compared with those of pure water clusters show the influence of fenchone's topology. Specifically, all observed hydrates except one show two water molecules binding to fenchone through each oxygen lone pair. The observation of several water arrangements for fenchone-(H2O)4-7 complexes highlights water adaptability and provides insight into the solvation process.

A Many-Body Perspective of Nuclear Quantum Effects in Aqueous Clusters.

Nuclear quantum effects play an important role in the structure and thermodynamics of aqueous systems. By performing a many-body expansion with nuclear-electronic orbital (NEO) theory, we show that proton quantization can give rise to significant energetic contributions for many-body interactions spanning several molecules in single-point energy calculations of water clusters. Although zero-point motion produces a large increase in energy at the one-body level, nuclear quantum effects serve to stabilize higher-order molecular interactions. These results are significant because they demonstrate that nuclear quantum effects play a nontrivial role in many-body interactions of aqueous systems. Our approach also provides a pathway for incorporating nuclear quantum effects into water potential energy surfaces. The NEO approach is advantageous for many-body expansion analyses because it includes nuclear quantum effects directly in the energies.

Photochemistry of micro-solvated benzonitrile complexes with water/ammonia bordering on the formation of icy grains

Polycyclic aromatic hydrocarbons (PAHs) act as condensation nuclei for water/ammonia molecules forming icy water clusters. In the context of small aromatic rings, we have theoretically examined complexes of benzonitrile with water/ammonia molecules in order to investigate the photochemical kinetics of the icy grain formation. First, we obtain the structure of energetically stable complexes containing different H-bonding patterns and analyze their effects in the infrared (IR) and vacuum ultraviolet (VUV) spectra, before and after ionization. Second, we evaluate the H-bonding reorientation kinetics of the complexes at low temperatures, which indicates that the process involving water occurs faster than the corresponding process involving ammonia. Finally, the thermal rate constants indicate which configurations are the most likely to be ionized under vacuum ultraviolet (VUV) irradiation. Our results are consistent with what has experimentally been observed for related complexes, and are useful as a starting point to investigate the process of the icy grains formation. This study provides insight into possible subsequent photochemical reactions occurring in the interstellar medium (ISM) or in jet-cooled molecular complexes.

Behaviour of RC Beam Using Concrete Mixed With Magnetically Treated Water

The most important challenge for concrete construction is to improve the performance of concrete. In the last two decades, in Russia and China, a new technology, called magnetic water technology, has been used in making concrete. As per this technology, by passing water through a magnetic field, some of its physical properties tend to change and, as a result of such changes, the number of molecules in the water cluster decreases from 13 to 5 or 6, which cause a decrease in the surface tension of water, with an improvement in the workability and strength of concrete. Magnetic treatment of water increases the ion solubility and pH. The influence of magnetic flux changes the mode of calcium carbonate precipitation such that circular disc-shaped particles are formed rather than the dendritic (branching or tree like) particles observed in non-treated water. This technique is mostly used for the softening of water and, for the first time in this research, it has been adopted by the scientists for the production of concrete with improved strength. Some researchers hypothesize that magnetic treatment affects the nature of hydrogen bonds between water molecules which increases the pH and softens the water.

Competition between Water-Water Hydrogen Bonds and Water-π Bonds in Pyrene-Water Cluster Anions.

We present infrared spectra and density functional theory calculations of hydrated pyrene anion clusters with up to four water molecules. The experimental spectra were acquired by using infrared Ar messenger photodissociation spectroscopy. Water molecules form clusters on the surface of the pyrene, forming hydrogen bonds with the π-system. The structures of the water clusters and their interaction with the π-system are encoded in OH stretching vibrational modes. We find that the interactions between water molecules are stronger than the interactions between water molecules and the π-system. While all clusters show multiple conformers, three- and four-membered rings are the lowest energy structures in the larger hydrates.

In English

The total reorganization energy of the system and its components, the solvent reorganization energy and the transformation energy of reactants (water clusters [(H2O)nOH]-), during electrocatalytic hydrogen evolution on binary alloys of molybdenum with iron subgroup metals (Fe, Co, Ni) in an alkaline medium (30 wt. % NaOH solution) have been calculated. The calculated values of the solvent reorganization energy and the reorganization energy of water clusters are in agreement with the Marcus – Dogonadze – Kuznetsov theory. The dependence of the total reorganization energy of the system, the solvent reorganization energy, and the reorganization energy of discharging species (water clusters) on the electrolyte temperature has been calculated. It was shown that the total reorganization energy of the system and the activation energy of the electron-transfer reaction of electrocatalytic hydrogen evolution (HER) on binary alloys of molybdenum with iron subgroup metals in an alcaline vedium (30 wt. % NaOH solution) decrease linearly with increasing electrolyte temperature in the following order: Fe-54 at. % Mo &gt; Ni-54 at. % Mo &gt; Co-52 at. % Mo. The temperature dependences of the water cluster discharge reorganization energy and the activation energy on binary molybdenum alloys are linear and intersect in the boiling point region of 30 wt. % NaOH solution 384.7 K. At this temperature, the electrode process is limited by the diffusion of regenerating water clusters to the electrode surface. The calculated diffusion activation energy Ad is 9.9 kJ·mol–1. The value of the system reorganization energy lt is 39.8 kJ·mol–1, which is consistent with the theory of Markus – Dogonadze – Kuznetsov. Electrocatalytic activity of binary alloys of molybdenum with iron subgroup m

Transferable Water Potentials Using Equivariant Neural Networks.

Machine learning interatomic potentials (MLIPs) have emerged as a technique that promises quantum theory accuracy for reduced cost. It has been proposed [J. Chem. Phys. 2023, 158, 084111] that MLIPs trained on solely liquid water data cannot accurately transfer to the vapor-liquid equilibrium while recovering the many-body decomposition (MBD) analysis of gas-phase water clusters. This suggests that MLIPs do not directly learn the physically correct interactions of water molecules, limiting transferability. In this work, we show that MLIPs using equivariant architecture and trained on 3200 liquid water structures reproduces liquid-phase water properties (e.g., density within 0.003 g/cm3 between 230 and 365 K), vapor-liquid equilibrium properties up to 550 K, the MBD analysis of gas-phase water cluster up to six-body interactions, and the relative energy and the vibrational density of states of ice phases. We show that potentials developed using equivariant MLIPs allow transferability for arbitrary phases of water that remain stable in nanosecond long simulations.

Integration of geoelectrical, hydrochemical and geothermal data to identify the origin of thermal water in the foothills of the Tlemcen mountains, Northwestern Algeria

In previous studies, the mean geothermal gradient of the Tlemcen region has been estimated as low (3.7°C/100m). The existing boreholes in the Remchi plain (North of the Tlemcen Mountains) reveal thermal waters (26-48°C) and a remarkable artesianism. To understand the hydrodynamics and origin of thermalism of this groundwater, we merged geophysical and physical-chemical data. Geophysical data allowed us to improve the resolution of the fault network, to estimate the thickness of various sandstone beds connected with the thermal reservoir and to delimit the productive aquifer. Chemical characteristics of waters have been used for a statistical analysis, which displayed two independent water clusters resulting from two hydrodynamic patterns throughout the aquifer. The hydrothermal analysis identifies the depth reached by water and the relationship between water circulation and the fault network. Comparison with previous studies allowed us to build a schematic geological model, which explains hydrodynamics, origin and role of this structure in the groundwater flow.

Networks of Hydrogen Bond Networks in Water Clusters.

Water clusters play a prominent role in atmospheric and solution chemistry. Numerous arrangements of protons, H-bond configurations or networks, shape the cluster properties. Studies of small water clusters by cryogenic scanning tunneling microscopy and high-resolution rovibrational spectroscopy have established proton rearrangement mechanisms forming pathways between H-bond networks. The mechanisms, concerted tunneling in particular, describe the local processes connecting pairs of configurations. Here, proton rearrangement networks mapping these transformations are defined and explored to provide a global view of the H-bond configurations in clusters. The networks are constructed for clusters of different sizes and structures. Their analysis reveals an odd-even effect with respect to the number of water molecules, exponential growth of the small-world character, bimodality of the degree distributions, and gapped assortativity of the networks. The last two properties signify the unexpected division of H-bond configurations into two classes according to their network connectivity. The results demonstrate qualitative differences between proton rearrangement mechanisms, suggest a strong influence of the cluster structure. The generated networks are of interest as real-world models for network rewiring; they establish an alternative platform for studies of proton rearrangements in H-bonded systems.

Keto-anthraquinone covalent organic framework for H2O2 photosynthesis with oxygen and alkaline water

Hydrogen peroxide photosynthesis suffers from insufficient catalytic activity due to the high energy barrier of hydrogen extraction from H2O. Herein, we report that mechanochemically synthesized keto-form anthraquinone covalent organic framework which is able to directly synthesize H2O2 (4784 μmol h−1 g−1 at λ > 400 nm) from oxygen and alkaline water (pH = 13) in the absence of any sacrificial reagents. The strong alkalinity resulted in the formation of OH-(H2O)n clusters in water, which were adsorbed on keto moieties within the framework and then dissociated into O2 and active hydrogen, because the energy barrier of hydrogen extraction was largely lowered. The produced hydrogen reacted with anthraquinone to generate anthrahydroquinone, which was subsequently oxidized by O2 to produce H2O2. This study ultimately sheds light on the importance of hydrogen extraction from H2O for H2O2 photosynthesis and demonstrates that H2O2 synthesis is achievable under alkaline conditions.