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Although small water clusters (SWCs) are important in many research fields, efficient methods of preparing SWCs are still rarely reported, which is mainly due to the lack of related materials and understanding of the molecular interaction mechanisms. In this study, a series of functional molecules were added in water to obtain small water cluster systems. The decreasing rate of the half-peak width in a sodium dodecyl sulfate (SDS)–water system reaches ≈20% at 0.05 mM from 17O nuclear magnetic resonance (NMR) results. Based on density functional theory (DFT) and molecular dynamics (MD) simulation calculation, it can be concluded that functional molecules with stronger negative electrostatic potential (ESP) and higher hydrophilicity have a stronger ability to destroy big water clusters. Notably, the concentrations of our selected molecule systems are one to two magnitudes lower than that of previous reports. This study provides a promising way to optimize aqueous systems in various fields such as oilfield development, protein stability, and metal anti-corrosion.

In the atmosphere, water in all phases is ubiquitous and plays important roles in catalyzing atmospheric chemical reactions, participating in cluster formation and affecting the composition of aerosol particles. Direct measurements of water-containing clusters are limited because water is likely to evaporate before detection, and therefore, theoretical tools are needed to study hydration in the atmosphere. We have studied thermodynamics and population dynamics of the hydration of different atmospherically relevant base monomers as well as sulfuric acid–base pairs. The hydration ability of a base seems to follow in the order of gas-phase base strength whereas hydration ability of acid–base pairs, and thus clusters, is related to the number of hydrogen binding sites. Proton transfer reactions at water–air interfaces are important in many environmental and biological systems, but a deeper understanding of their mechanisms remain elusive. By studying thermodynamics of proton transfer reactions in clusters containing up to 20 water molecules and a base molecule, we found that that the ability of a base to accept a proton in a water cluster is related to the aqueous-phase basicity. We also studied the second deprotonation reaction of a sulfuric acid in hydrated acid–base clusters and found that sulfate formation is most favorable in the presence of dimethylamine. Molecular properties related to the proton transfer ability in water clusters are discussed.

Theoretical descriptions of excited state proton transfer (ESPT) have had various degrees of success. This work presents a theoretical description of the photodissociation of the 7-hydroxyflavylium cation (7-HF), the fundamental chromophoric moiety of anthocyanin natural plant pigments. ESPT of 7-HF is promoted by a significant shift of charge away from the OH group in the first singlet excited state, leading smoothly to the excited conjugate base and a protonated water cluster. Several factors contribute to the consistency of the results of the present study: (1) the theoretical approach (TD-DFT with the B3-LYP functional and def2-TZVP basis set utilizing Grimme's D3 dispersion correction); (2) the modeling of the solvent effect combining hydrogen bonding of the photoacid to a cluster of discrete water molecules in a water-like continuum solvent (COSMO); (3) the large S1 -S2 energy gap of flavylium cations; and (4) the electrostatics of the ESPT in which a proton is transferred from a cationic photoacid to water without Coulombic interaction between the proton and the conjugate base.

Producción Científica, The structure of butyl carbamate and of its complex with water generated in a supersonic expansion has been characterized by Fourier transform microwave spectroscopy. Up to 13 low-energy conformations of the monomer have been predicted which differ in the relative orientation of the butyl chain and the amide group. However, only three conformations have been observed experimentally. The remaining low energy conformers are expected to interconvert into the observed rotamers through collisional relaxation processes in the supersonic jet. The values of the C-O-Cα-Cβ dihedral angle observed for the two most stable conformers of butyl carbamate, with extended configurations, can be directly correlated with the values of this angle in the two experimentally observed conformers of the shorter-chain molecule, ethyl carbamate. The less stable form shows a weak C-H...O=C intramolecular hydrogen bond from the terminal methyl group to the carbamate C=O group, stabilizing a folded configuration. For the most stable butyl carbamate monomer the complex with one molecule of water has been observed. In that complex the water molecule attaches to the amide group in a cyclic arrangement using two hydrogen bonds. The results indicate that water does not substantially alter the conformational behavior of butyl carbamate., Ministerio de economia, industria y competitividad CTQ2016-75253-P

Given the piecewise approach to modeling intermolecular interactions for force fields, they can be difficult to parameterize since they are fit to data like total energies that only indirectly connect to their separable functional forms. Furthermore, by neglecting certain types of molecular interactions such as charge penetration and charge transfer, most classical force fields must rely on, but do not always demonstrate, how cancellation of errors occurs among the remaining molecular interactions accounted for such as exchange repulsion, electrostatics, and polarization. In this work we present the first generation of the (many-body) MB-UCB force field that explicitly accounts for the decomposed molecular interactions commensurate with a variational energy decomposition analysis, including charge transfer, with force field design choices that reduce the computational expense of the MB-UCB potential while remaining accurate. We optimize parameters using only single water molecule and water cluster data up through pentamers, with no fitting to condensed phase data, and we demonstrate that high accuracy is maintained when the force field is subsequently validated against conformational energies of larger water cluster data sets, radial distribution functions of the liquid phase, and the temperature dependence of thermodynamic and transport water properties. We conclude that MB-UCB is comparable in performance to MB-Pol, but is less expensive and more transferable by eliminating the need to represent short-ranged interactions through large parameter fits to high order polynomials.

Understanding water distribution behaviors plays an essential role in shale gas development due to the hydraulic fracturing technology. In this study, water vapor adsorption isotherms were measured for Upper Triassic Yanchang and Lower Silurian Longmaxi samples at 288.15 K, 298.15 K and 308.15 K to investigate the adsorption behaviors of water on shale. For a description of adsorption process, a Dent’s model provides an estimate of primary and secondary adsorption sites of water adsorption. The effects of temperature, shale mineralogy, and water distribution were discussed. The results show that temperature has a negative effect on water vapor adsorption. Adsorption capacities of primary and secondary sites decrease with increasing temperature. Water vapor adsorption capacity is tightly associated with clay content, whereas water vapor adsorption has no significant relationship with total organic carbon (TOC). Normalized water vapor adsorption content also has no significant relationship with TOC, which indicates no obvious correlation between water vapor adsorption and TOC content. The inter-crystal pores of clay minerals provide significant specific surface for gas adsorption in shale. At low relative pressure, a large number of water molecules adsorb on the primary sites. At high relative vapor pressure, most of the primary sites have been occupied, so that the secondary adsorption sites will be utilized. Therefore, due to relative weak binding energies in secondary adsorption sites, water cluster are formed in micro-pores of shale. As relative vapor pressure increases, capillary condensation gradually predominates over the adsorption. The study will reveal mechanism of water adsorption and distribution characteristics on shale and provide some foundation for geological reserve estimation and shale gas recovery prediction.

Three novel metal-organic complexes, formulated as [Cu2(2-HBA)2(bimb)4] (1), {[Cd(CEDA)(bimb)]·H2O}n (2), and {[Ag2(bimb)2]·(1,4-CDA)·13H2O} (3) (bimb = 1,2-bis((1H-imidazole-1-yl)methyl)benzene; 2-HBA = 2-hydroxybenzoic acid; CEDA = cyclohex-4-ene-1,2-dicarboxylic acid; 1,4-CDA = cyclohexane-1,4-dicarboxylic acid), were synthesized by self-assembly of mixed ligands with Cu(II), Cd(II), and Ag(I) under hydrothermal conditions and characterized by means of single-crystal X-ray diffraction, X-ray powder diffraction, infrared spectra, thermogravimetric analysis, fluorescence spectra and UV–vis absorption spectra. 1 is shown as a 0D structure, which is formed by Cu2+, 2-HBA ligands and bimb ligands. 2 displays a 1D ladder structure, which is built by Cd2+, CEDA ligands and bimb ligands, and it is assembled into 2D structure by hydrogen bonding. 3 possesses a 0D [Ag(bimb)]2 dimer which is assembled into 3D structure by the Ag O weak interaction and hydrogen bonding. Interestingly, a rare 13-core water cluster participates in forming the network of 3. The UV–vis spectrum and luminescence properties were also studied and discussed.

Using the multiphase lattice Boltzmann method (LBM), the liquid water transport dynamics is simulated in a gas diffusion layer (GDL) of polymer electrolyte membrane fuel cells (PEMFCs). The effect of rib structure on the water invasion process in the micro-porous GDL is explored by comparing the two cases, i.e., with rib and without rib structures. The liquid water distribution and water saturation profile are presented to determine the wetting mechanism in the GDL. The results show that the liquid water transport in the GDL is strongly governed by capillary force and the rib structure plays a significant role on water distribution and water transport behavior in the GDL. Comparison of two cases confirms that the rib structure influences on the location of water breakthrough. The liquid water distribution and water saturation profile indicate that the high resistance force underneath the rib suppresses the growth of water cluster, resulting in the change of flow path. After water breakthrough, the liquid water distribution under the channel has little variation, whereas that under the rib continues to change. The predicted value of effective permeability is in good agreement with Carman-Kozeny correlation and experimental results in the literature. The results suggest that the LBM approach is an effective tool to investigate the water transport behavior in the GDL.

Previous studies have shown that the use of a 20 keV water cluster beam as a primary beam for the analysis of organic and bio-organic systems resulted in a 10-100 times increase in positive molecular ion yield for a range of typical analytes compared to C60 and argon cluster beams. This resulted in increased sensitivity to important lipid molecules in the bioimaging of rat brain. Building on these studies, the present work compares 40 and 70 keV water cluster beams with cluster beams composed of pure argon, argon and 10%CO2, and pure CO2. First, as previously, we show that for E/nucleon about 0.3 eV/nucleon water and nonwater containing cluster beams generate very similar ion yields, but below this value, the water beams yields of BOTH negative and positive "molecular" ions increase, in many cases reaching a maximum in the

Poly-lactic acid (PLA) is widely used as a controlled drug release material and the diffusion property of water within the polymer matrix is closely related to the drug release profile. This paper studies the water diffusion in PLA by molecular dynamic simulations. Free volume analysis indicates that water molecules are expected to fill in the free volumes of the polymer matrix forming water clusters at low water content. Along with the increase of the water concentration, the polymer starts to swell and the density of the system starts to drop. Due to the high mobility of water within water cluster, the calculated diffusion coefficient dramatically increases along with the incensement of water content. Thus, we conclude that the diffusion of water is a self-accelerate process, with higher mobility of water in the case where more water exists.

A new series of six isostructural molecular solids of the composition [{Al(H2O)6}{Ln(pda)3}].10H2O where Ln = Sm, Eu, Gd, Tb, Dy and Yb have been synthesized and structurally characterised. All the solids are built of three major building blocks: the lanthanide dipicolinate anion, {Ln(pda)3}3−, the counter cation, {Al(H2O)6}3+ and a hexameric water cluster in chair form. The cations and the anions supramolecularly aggregate forming a 2D H-bonded sheet; the sheets are further stabilised through hexameric water clusters in chair form and water molecules. The crystals containing Sm, Eu, Tb and Dy showed characteristic emission of lanthanide ions.

The hydrothermal reaction of NiSO4·6H2O and 4,4′-bis(1-imidazolyl)bipheny (bibp) has afforded a new nickel complex, {[Ni4(µ3-OH)4(µ4-SO4)(bibp)4](OH)2·12H2O}n (1). The Ni(II) centers are bridged by µ3-OH- anions into cubic [Ni4(µ3-OH)4] units, which are connected by bibp ligands and µ4-SO42- anions into a double-walled 3D framework with channels along c direction. Unusual 1D water cages with a repeat of vase-like water cluster are trapped in the channels. Magnetic studies reveal ferromagnetic behavior for complex 1, and the thermal property of 1 was also studied.

Real time in-situ observation by small-angle neutron scattering (SANS) was performed to observe the development of microstructure in a polyelectrolyte membrane packed in a polymer electrolyte fuel cell (PEFC) during initial conditioning. By utilizing the excellent penetrability of neutrons, an operating fuel cell was studied. SANS originating from the membrane was analyzed to determine the water cluster radius (Rc) and its number density (ρc). We found that Rc increased and ρc decreased, as the load current was increased during initial conditioning. The maximum Rc achieved at high current density became larger as the conditioning cycle proceeded. In this process, two water clusters combined and the connectivity of proton conduction channels was enhanced. As a consequence, was reduced ohmic loss, which was detected by using a special segmented electrode cell covering the cell section corresponding to that observed by SANS. Keywords: Small-angle neutron scattering, Polymer electrolyte fuel cell, Aging effect, Connectivity of proton conduction channel

Electron attachment onto water clusters to form water cluster anions is studied by varying the point of electron attachment along a molecular beam axis and probing the produced cluster anions using photoelectron spectroscopy. The results show that the point of electron attachment has a clear effect on the final distribution of isomers for a cluster containing 78 water molecules, with isomer I formed preferentially near the start of the expansion and isomer II formed preferentially once the molecular beam has progressed for several millimetres. These changes can be accounted for by the cluster growth rate along the beam. Near the start of the expansion, cluster growth is proceeding rapidly with condensing water molecules solvating the electron, while further along the expansion, the growth has terminated and electrons are attached to large and cold preformed clusters, leading to the isomer associated with a loosely bound surface state.

The application of an external electric field to a solution alters the orientational probability distribution of water molecules. Hence, the forces exerted by the solvent on the charged groups of the solute are modified. In this study, the mechanisms underlying the dependence of these forces on the external electric field are proposed. To evaluate the accuracy of these hypotheses, an external electric field is applied to a water cluster containing a solute with electric dipoles and/or charges, and the forces of the solvents acting on the dipoles and charges are calculated from the trajectories obtained in molecular dynamics simulations. The simulation results are found to be consistent with the proposed mechanisms.

We investigate water desorption from hydrophobic surfaces using two curved Ag single crystals centered at (111) and (001) apices. On these types of crystals the step density gradually increases along the curvature, allowing us to probe large ranges of surface structures in between the (001), (111) and (110) planes. Subtle differences in desorption of submonolayer water coverages point toward structure dependencies in water cluster nucleation. The B-type step on hydrophobic Ag binds water structures more strongly than adjacent (111) planes, leading to preferred desorption from steps. This driving force is smaller for A-type steps on (111) terraces. The A′-type step flanked by (001) terraces shows no indication of preferred desorption from steps. Extrapolation to the (311) surface, not contained within either curved surface, demonstrates that both A- and A′-type steps can be regarded chemically identical for water desorption. The different trends in desorption temperature on the two crystals can thus be attributed to stronger water adsorption at (001) planes than at (111) planes and identical to adsorption at the step. These results show that our approach to studying the structure dependence of water desorption is sensitive to variations in desorption energy smaller than ‘chemical accuracy’, i.e. 1 kcal mol−1.

The common understanding of zeolite acidity is based on Lowenstein's rule, which states that Al-O-Al aluminium pairs are forbidden in zeolites. This rule is generally accepted to be inviolate in zeolites. However, recent computational research using a 0 K DFT model has suggested that the rule is violated for the acid form of several zeolites under anhydrous conditions [Fletcher et al., Chem. Sci., 8, (2017), 7483]. The effect of water loading on the preferred aluminium distribution in zeolites, however, has so far not been taken into account. In this article, we show by way of ab initio molecular dynamics simulations that Lowenstein's rule is obeyed under high water solvation for acid chabazite (H-CHA) but disobeyed under anhydrous conditions. We find that varying the water loading in the pores leads to dramatic effects on the structure of the active sites and the dynamics of solvation. The solvation of Bronsted protons in the surrounding water was found to be the energetic driving force for the preferred Lowenstein Al distribution and this driving force is absent in non-Lowenstein (Al-O(H)-Al) moieties. The preference for solvated protons further implies that the catalytically active species in zeolites is a protonated water cluster, rather than a framework Bronsted site. Hence, an accurate treatment of the solvation conditions is crucial to capture the behaviour of zeolites and to properly connect simulations to experiments. This work should lead to a change in modelling paradigm for zeolites, from single molecules towards high solvation models where appropriate.

15‐crown‐5 ether (15C5) and its complexes with water (w) have been studied using broadband Fourier transform microwave spectroscopy in a supersonic jet. A new conformer of 15C5 has been observed and established as the new global minimum out of a total of nine isolated structures. In addition, two 15C5‐w and two 15C5‐w2 clusters have been observed. The cluster structures have been unambiguously identified through the observation of water 18O isotopologue spectra. In all the clusters, at least one water molecule, located close to the axis of the 15C5 ring, interacts through two simultaneous hydrogen bonds to the endocyclic oxygen atoms. This interaction reshapes the 15C5 ring to reduce its rich conformational landscape to only two open structures, related to those found in complexes with Li+ or Na+ ions. In the most abundant 15C5‐w2 form, the two water molecules repeat the same interaction scheme while binding to opposite sides of the ring. In the second most abundant dihydrated form the two water molecules lie on the same side of the ring. This finding is exceptionally rare because water‐water interactions typically prevail over the formation of additional solutewater contacts, and it showcases the particular binding features of crown ethers., Ministerio de economia, industria y competitividad CTQ2016-75253-P

Graphitic carbon nitride (g-C3N4) is a novel two-dimensional, nitrogen-doped carbon material with various applications in many fields. Recently, g-C3N4 has exhibited excellent ability in separations. In this work, mechanisms of water and ion permeation across nanoporous g-C3N4 membranes with different pore diameters were studied using non-equilibrium molecular dynamics simulations. The water conduction rates derived from our simulations are in good agreement with previous experimental data. Due to the nanoscale confinement, we observe a stacked water cluster structure within the narrowest nanochannel. Similar structures are obscure as the increase of the nanochannel sizes. For desalination purposes, we find that the nanoporous g-C3N4 membrane with the desired opening may completely reject calcium and chloride ions, whereas sieve out monovalent cations with acceptable rejection rates (over 70%). This work provides molecular insight into the mechanism of water and ion transport through nanoporous g-C3N4, which strongly supports that this novel material is a promising candidate for developing selective membrane for water desalination.

This work is dedicated to the theoretical investigation of the influence of water clusters’ organisation and size on the electronic spectrum of an interacting benzene (Bz) molecule using both TD-DFT and CASPT2 approaches. Two series of geometries, namely $$Geo_{IEI}$$ and $$Geo_{IED}$$ were extracted from two Bz-hexagonal ice configurations leading to maximum and minimum ionization energies respectively. An appropriate basis set containing atomic diffuse and polarisation orbitals and describing the Rydberg states of Bz was determined. The TD-DFT approach was carefully benchmarked against CASPT2 results for the smallest systems. Despite some discrepancies, the trends were found to be similar at both levels of theory: the positions and intensities of the main $$\pi \rightarrow \pi ^{\star }$$ transitions were found slightly split due to symmetry breaking. For the smallest systems, our results clearly show the dependence of the electronic transitions on the clusters’ structures. Of particular interest, low energy transitions of non negligible oscillator strength from a Bz $$\pi$$ orbital to a virtual orbital of Rydberg character, also involving atomic diffuse functions and partially expanded on the water cluster, were found for the $$Geo_{IED}$$ series. The energies of such transitions were determined to be more than 2 eV below the ionization potential of Bz. When the cluster’s size increases, similar transitions were found for all structures, the virtual orbitals becoming mainly developed on the H atoms of the water molecules at the edge of the cluster. Given their nature and energy, such transitions could play a role in the photochemistry of aromatic species in interaction with water clusters or ice, such processes being of astrophysical interest.

Promoting fluid transportation in porous media has important applications in energy, pedology, bioscience, etc. For this purpose, one effective way is to prevent swelling through surface modification, however, it is far from enough in real cases, such as ultra-low permeability reservoirs and tight oils. In this study, we considered the comprehensive effects of inhibiting clay swelling, flocculation performance, reducing water clusters and interfacial tension and developed a series of imidazole-based tetrafluoroborate ionic liquids (ILs) with different lengths of alkyl chains. Through measurements of anti-swelling rates, XRD, SEM, 17O NMR, molecular dynamics simulation, zeta potential, flocculation evaluation, interfacial tension and a core flooding experiment based on ultra-low permeability reservoirs, the relationships between the molecular structure and physicochemical properties of ILs have been revealed. Interestingly, one of the selected ILs, imidazole-based tetrafluoroborate ILs (C8-OMImBF4), shows excellent performance, which is helpful to design an effective strategy in promoting fluid transportation in narrow spaces.

Chemical reactivity and sorption in zeolites are coupled to confinement and-to a lesser extent-to the acid strength of Brønsted acid sites (BAS). In presence of water the zeolite Brønsted acid sites eventually convert into hydronium ions. The gradual transition from zeolite Brønsted acid sites to hydronium ions in zeolites of varying pore size is examined by ab initio molecular dynamics combined with enhanced sampling based on Well-Tempered Metadynamics and a recently developed set of collective variables. While at low water content (1-2 water/BAS) the acidic protons prefer to be shared between zeolites and water, higher water contents (n > 2) invariably lead to solvation of the protons within a localized water cluster adjacent to the BAS. At low water loadings the standard free energy of the formed complexes is dominated by enthalpy and is associated with the acid strength of the BAS and the space around the site. Conversely, the entropy increases linearly with the concentration of waters in the pores, favors proton solvation and is independent of the pore size/shape., Nature Communications, 12 (1), ISSN:2041-1723

In this paper, we present a comparative analysis of the solid state structures of three well-resolved hydrates of macrocyclic host molecules 1a, 1b, and 2 containing an intrannular amide-aryl substituent (lariat arm) connected to a fixed 26-membered ring in a normal (-NHCOAr, hosts 1a and 1b) or reverse manner (-CONHAr, host 2). Despite different chemical structures, these hosts crystallize as isostructural tetrahydrates in the same P-1 space group. Moreover, their crystals exhibit identical hydrogen bond motifs resulting in a stabilization of an almost identical unusual octameric water cluster built from the cyclic tetramer core and four water molecules, attached sequentially in an “up-and-down” manner. Further analysis reveals that, among the series, the structure of host 2 provides the most suitable environment for the accommodation of this type of water cluster.

The oxidation reaction of thiamine (vitamin B1) to thiochrome was investigated by DFT calculations. Three reaction systems, [A] thiamine + methyl peroxy radical + (H2O)8, [B] thiamine + cyanogen bromide + HO-(H2O)8 and [C] thiamine + mercury(ii) chloride + HO-(H2O)8, were investigated. wB97X-D/6-311+G** for [A] and [B] and wB97X-D/SDD&6-311(+)G** for [C] geometry optimizations were carried out with the solvent effect (water). The effect is of the self-consistent reaction field (SCRF) with the polarizable continuum model (PCM). In [A], the H3C-O2˙ adduct of thiamine undergoes simultaneous cleavage of the C-H and O-O bonds, leading to a very stable 2(3H)-thiazolone intermediate. The same intermediate was obtained after the cleavage of the C-H and O-H bonds of the HO adduct of thiamine in [B] and [C]. After the formation of the key intermediate, the N-protonated thiochrome was afforded via three steps. In reflection of the water-soluble character of vitamin B1, proton transfers along hydrogen bonds of the water cluster enhance those steps.

Since molecular cluster ion beams are expected to have various chemical effects, they are promising candidates for improving the secondary ion yield of Tof-SIMS. However, in order to clarify the effect and its mechanism, it is necessary to generate molecular cluster ion beams with various chemical properties and systematically examine it. In this study, we have established a method to stably form various molecular cluster ion beams from relatively small amounts of liquid materials for a long time by the bubbling method. Furthermore, we applied the cluster ion beams of water, methanol, methane, and benzene to the primary beam of SIMS and compared the molecular ion yields of aspartic acid. The effect of enhancing the yields of [M+H]+ ion of aspartic acid was found to be the largest for the water cluster and small for the methane and benzene clusters. These results indicate that the chemical effect contributes to the desorption/ionization process of organic molecules by the molecular cluster ion beam.

We report a Many Body Energy (MBE) analysis of aqueous ionic clusters containing anions and cations at the two opposite ends of the Hofmeister series, viz. the kosmotropes Ca2+ and SO42− and the chaotropes NH4+ and ClO4−, with 9 water molecules to quantify how these ions alter the interaction between the water molecules in their immediate surroundings. We specifically aim at quantifying how various ions (depending on their position in the Hofmeister series) affect the interaction between the surrounding water molecules and probe whether there is a qualitatively different behavior between kosmotropic vs. chaotropic ions. The current results when compared to the ones reported earlier for water clusters [J. P. Heindel and S. S. Xantheas, J. Chem. Theor. Comput., 2020, 16, 6843–6855] as well as for alkali metal and halide ion aqueous clusters of the same size [J. P. Heindel and S. S. Xantheas, J. Chem. Theor. Comput., 2021, 17, 2200–2216], which lie in the middle of the Hofmeister series, offer a complete account of the effect an ion across the Hofmeister series from “kosmotropes” to “chaotropes” has on the interaction between the neighboring water molecules. Through this analysis, noteworthy differences between the MBE of kosmotropes and chaotropes were identified. The MBE of kosmotropes is dominated by ion–water interactions that extend beyond the 4-body term, the rank at which the MBE of pure water converges. The percentage contribution of the 2-B term to the total cluster binding energy is noticeably larger. The disruption of the hydrogen bonded network due to the dominant ion–water interactions results in weak, unfavorable water–water interactions. The MBE for chaotropes, on the other hand, was found to converge more quickly as it more closely resembles that of pure water clusters. Chaotropes exhibit weaker overall binding energies and weaker ion–water interactions in favor of water–water interactions, somewhat recovering the pattern of the 2-4 body terms exemplified by pure water clusters. A remarkable anti-correlation between the 2-B ion–water (I–W) and water–water (W–W) interactions as well as between the 3-B (I–W–W) and (I–W) interactions was found for both kosmotropic and chaotropic ions. This anti-correlation is linear for both monatomic anions and monatomic cations, suggesting the existence of underlying physical mechanisms that were previously unexplored. The consideration of two different structural arrangements (ion inside and outside of a water cluster) suggests that fully solvated (ion inside) chaotropes disrupt the hydrogen bonding network in a similar manner to partially solvated (ion outside) kosmotropes and offers useful insights into the modeling requirements of bulk vs. interfacial ion solvation. It is noteworthy that the 2-B contribution to the total Basis Set Superposition Error (BSSE) correction for both kosmotropic and chaotropic ions follows the universal erf profile vs. intermolecular distance previously reported for pure water, halide ion–water and alkali metal ion–water clusters. When scaled for the corresponding dimer energies and distances, a single profile fits the current results together with all previously reported ones for pure water and halide water clusters. This finding lends further support to schemes for accurately estimating the 2-B BSSE correction in condensed environments.

We analyzed the interactions present in complexes that acetone, azomethane, dimethylamine, dimethyl ether, methyl acetate, and oxirane form with 39 different (H2O)n clusters (n = 1-10). A random generation of configurations and a subsequent screening procedure were employed to sample representative interactions. Using quantum chemical computations, we calculated the associated binding energies, which range from -0.19 to -10.76 kcal/mol at the DLPNO-CCSD(T)/CBS level. It was found that the binding energies can be understood in terms of various factors, including the water cluster size, the nature of the organic molecule, and the type of hydrogen bond donor. We find that the most stable complexes often arise from a combination of a strong hydrogen bond plus a secondary interaction between the organic molecule and the water cluster.