NaCl Nucleation Research Articles

Is the Local Ion Density Sufficient to Drive NaCl Nucleation from the Melt and Aqueous Solution?

Even though nucleation is ubiquitous in different science and engineering problems, investigating nucleation is extremely difficult due to the complicated ranges of time and length scales involved. In this work, we simulate NaCl nucleation in both molten and aqueous environments using enhanced sampling of all-atom molecular dynamics with deep-learning-based estimation of reaction coordinates. By incorporating various structural order parameters and learning the reaction coordinate as a function thereof, we achieve significantly improved sampling relative to traditional ad hoc descriptions of what drives nucleation, particularly in an aqueous medium. Our results reveal a one-step nucleation mechanism in both environments, with reaction coordinate analysis highlighting the importance of local ion density in distinguishing solid and liquid states. However, although fluctuations in the local ion density are necessary to drive nucleation, they are not sufficient. Our analysis shows that near the transition states, descriptors such as enthalpy and local structure become crucial. Our protocol proposed here enables robust nucleation analysis and phase sampling and could offer insights into nucleation mechanisms for generic small molecules in different environments.

Atomic scale insights into NaCl nucleation in nanoconfined environments.

In this work we examine the nucleation from NaCl aqueous solutions within nano-confined environments, employing enhanced sampling molecular dynamics simulations integrated with machine learning-derived reaction coordinates. Through our simulations, we successfully induce phase transitions between solid, liquid, and a hydrated phase, typically observed at lower temperatures in bulk environments. Interestingly, while generally speaking nano-confinement serves to stabilize the solid phase and elevate melting points, there are subtle variations in the thermodynamics of competing phases with the precise extent of confinement. Our simulations explain these findings by underscoring the significant role of water, alongside ion aggregation and subtle, anisotropic dielectric behavior, in driving nucleation within nano-confined environments. This report thus provides a framework for sampling, analyzing and understanding nucleation processes under nano-confinement.

Molecular dynamics study with COMPASS II forcefield on nucleation and growth mechanism of sodium chloride in supercritical water

Supercritical water gasification (SCWG) is a promising technology for converting and utilizing high-salt organic waste, while salt deposition problems seriously hinder its industrial application. In this work, the formation and evolution of sodium chloride (NaCl) clusters in supercritical water (SCW) at the range of (0.1–0.3) g·cm−3 and (673–1073) K are investigated using molecular dynamics simulations. The findings demonstrate that the nucleation and growth process can be divided into three stages: ion pairs, small ionic clusters, and large clusters. Nucleation processes are completed within the initial 20 ps, with the nucleation rate of NaCl in SCW reaching magnitudes of 1036 m−3·s−1, exhibiting an increasing trend with temperature and density. Lower densities and higher temperatures facilitate NaCl nucleation, and clusters grown at lower densities exhibit a more compact structure.

CNT effective interfacial energy and pre-exponential kinetic factor from measured NaCl crystal nucleation time distributions in contracting microdroplets.

Nucleation, the birth of a stable cluster from a disorder, is inherently stochastic. Yet up to date, there are no quantitative studies on NaCl nucleation that accounts for its stochastic nature. Here, we report the first stochastic treatment of NaCl-water nucleation kinetics. Using a recently developed microfluidic system and evaporation model, our measured interfacial energies extracted from a modified Poisson distribution of nucleation time show an excellent agreement with theoretical predictions. Furthermore, analysis of nucleation parameters in 0.5, 1.5, and 5.5 pl microdroplets reveals an interesting interplay between confinement effects and shifting of nucleation mechanisms. Overall, our findings highlight the need to treat nucleation stochastically rather than deterministically to bridge the gap between theory and experiment.

An investigation of the kinetics and thermodynamics of NaCl nucleation through composite clusters.

Having a good understanding of nucleation is critical for the control of many important processes, such as polymorph selection during crystallization. However, a complete picture of the molecular-level mechanisms of nucleation remains elusive. In this work, we take an in-depth look at the NaCl homogeneous nucleation mechanism through thermodynamics. Distinguished from the classical nucleation theory, we calculate the free energy of nucleation as a function of two nucleus size coordinates: crystalline and amorphous cluster sizes. The free energy surface reveals a thermodynamic preference for a nonclassical mechanism of nucleation through a composite cluster, where the crystalline nucleus is surrounded by an amorphous layer. The thickness of the amorphous layer increases with an increase in supersaturation. The computed free energy landscape agrees well with the composite cluster-free energy model, through which phase specific thermodynamic properties are evaluated. As the supersaturation increases, there is a change in stability of the amorphous phase relative to the solution phase, resulting in a change from one-step to two-step mechanism, seen clearly from the free energy profile along the minimum free energy path crossing the transition curve. By obtaining phase-specific diffusion coefficients, we construct the full mesoscopic model and present a clear roadmap for NaCl nucleation.

Hydration breaking and chemical ordering in a levitated NaCl solution droplet beyond the metastable zone width limit: evidence for the early stage of two-step nucleation.

For over two decades, NaCl nucleation from a supersaturated aqueous solution has been predicted to occur via a two-step nucleation (TSN) mechanism, i.e., two sequential events, the formation of locally dense liquid regions followed by structural ordering. However, the formation of dense liquid regions in the very early stage of TSN has never been experimentally observed. By using a state-of-the-art technique, a combination of electrostatic levitation (ESL) and in situ synchrotron X-ray and Raman scatterings, we find experimental evidence that indicates the formation of dense liquid regions in NaCl bulk solution at an unprecedentedly high level of supersaturation (S = 2.31). As supersaturation increases, evolution of ion clusters leads to chemical ordering, but no topological ordering, which is a precursor for forming the dense disordered regions of ion clusters at the early stage of TSN. Moreover, as the ion clusters proceed to evolve under highly supersaturated conditions, we observe the breakage of the water hydration structure indicating the stability limit of the dense liquid regions, and thus leading to nucleation. The evolution of solute clusters and breakage of hydration in highly supersaturated NaCl bulk solution will provide new insights into the detailed mechanism of TSN for many other aqueous solutions.

Homogeneous nucleation of NaCl in supersaturated solutions.

The seeding method is an approximate approach to investigate nucleation that combines molecular dynamics simulations with classical nucleation theory. Recently, this technique has been successfully implemented in a broad range of nucleation studies. However, its accuracy is subject to the arbitrary choice of the order parameter threshold used to distinguish liquid-like from solid-like molecules. We revisit here the crystallization of NaCl from a supersaturated brine solution and show that consistency between seeding and rigorous methods, like Forward Flux Sampling (from previous work) or spontaneous crystallization (from this work), is achieved by following a mislabelling criterion to select such threshold (i.e. equaling the fraction of the mislabelled particles in the bulk parent and nucleating phases). This work supports the use of seeding to obtain fast and reasonably accurate nucleation rate estimates and the mislabelling criterion as one giving the relevant cluster size for classical nucleation theory in crystallization studies.

Membrane-Assisted Crystallization: A Molecular View of NaCl Nucleation and Growth

Membrane-assisted crystallization, aiming to induce supersaturation in a solution, has been successfully tested in the crystallization of ionic salts, low molecular organic acids, and proteins. Membrane crystallization is an emerging membrane process with the capability to simultaneously extract fresh water and valuable components from various streams. Successful application of crystallization for produced water treatment, seawater desalination, and salt recovery has been demonstrated. Recently, membrane crystallization has been developed to recover valuable minerals from highly concentrated solutions, since the recovery of high-quality minerals is expected to impact agriculture, pharmaceuticals, and household activities. In this work, molecular dynamics simulations were used to study the crystal nucleation and growth of sodium chloride in bulk and with hydrophobic polymer surfaces of polyvinylidene fluoride (PVDF) and polypropylene (PP) at a supersaturated concentration of salt. In parallel, membrane crystallization experiments were performed utilizing the same polymeric membranes in order to compare the experimental results with the computational ones. Moreover, the comparison in terms of nucleation time between the crystallization of sodium chloride (NaCl) using the traditional evaporation process and the membrane-assisted crystallization process was performed. Here, with an integrated experimental–computational approach, we demonstrate that the PVDF and PP membranes assist the crystal growth for NaCl, speeding up crystal nucleation in comparison to the bulk solution and leading to smaller and regularly structured face-centered cubic lattice NaCl crystals. This results in a mutual validation between theoretical data and experimental findings and provides the stimuli to investigate other mono and bivalent crystals with a new class of materials in advanced membrane separations.

Communication: Nucleation rates of supersaturated aqueous NaCl using a polarizable force field.

In this work, we use molecular dynamics simulations with a polarizable force field, namely, the modified AH/BK3 model [J. Kolafa, J. Chem. Phys. 145, 204509 (2016)], in combination with the forward flux sampling technique, to calculate the rates of homogeneous nucleation of NaCl from supersaturated aqueous solutions at 298 K and 1 bar. A non-polarizable model that reproduces the experimental equilibrium solubility {AH/TIP4P-2005 of Benavides et al. [J. Chem. Phys. 147, 104501 (2017)]} is also used for comparison. Nucleation rates calculated from the polarizable force field are found to be in good agreement with experimental measurements, while the non-polarizable model severely underestimates the nucleation rates. These results, in combination with our earlier study of a different non-polarizable force field [H. Jiang et al., J. Chem. Phys. 148, 044505 (2018)], lead to the conclusion that nucleation rates are sensitive to the details of force fields, and a good representation of nucleation rates may not be feasible using available non-polarizable force fields, even if these reproduce the equilibrium salt solubility. Inclusion of polarization could be important for an accurate prediction of nucleation rates in salt solutions.

NaCl nucleation from brine in seeded simulations: Sources of uncertainty in rate estimates.

This work reexamines seeded simulation results for NaCl nucleation from a supersaturated aqueous solution at 298.15 K and 1 bar pressure. We present a linear regression approach for analyzing seeded simulation data that provides both nucleation rates and uncertainty estimates. Our results show that rates obtained from seeded simulations rely critically on a precise driving force for the model system. The driving force vs. solute concentration curve need not exactly reproduce that of the real system, but it should accurately describe the thermodynamic properties of the model system. We also show that rate estimates depend strongly on the nucleus size metric. We show that the rate estimates systematically increase as more stringent local order parameters are used to count members of a cluster and provide tentative suggestions for appropriate clustering criteria.

Manipulating Single Microdroplets of NaCl Solutions: Solvent Dissolution, Microcrystallization, and Crystal Morphology.

A new "three-micropipette manipulation technique" for forming, dehydrating, crystallizing, and resolvating nanograms of salt material has been developed to study supersaturated single microdroplets and microcrystals. This is the first report of studies that have measured in situ both supersaturation (as homogeneous nucleation) and saturation (as microcrystal redissolution) for single microdroplets of NaCl solution using the micropipette technique. This work reports a measure of the critical supersaturation concentration for homogeneous nucleation of NaCl (10.3 ± 0.3 M) at a supersaturation fraction of S = 1.9, the saturation concentration of NaCl in aqueous solution as measured with nanograms of material (5.5 ± 0.1 M), the diffusion coefficient for water in octanol, D = (1.96 ± 0.10) × 10-6 cm2/s, and the effect of the solvent's activity on dissolution kinetics. It is further shown that the same Epstein-Plesset (EP) model, which was originally developed for diffusion-controlled dissolution and uptake of gas, and successfully applied to liquid-in-liquid dissolution, can now also be applied to describe the diffusion-controlled uptake of water from a water-saturated environment using the extended activity-based model of Bitterfield et al. This aspect of the EP model has not previously been tested using single microdroplets. Finally, it is also reported how the water dissolution rate, rate of NaCl concentration change, resulting crystal structure, and the time frame of initial crystal growth are affected by changing the bathing medium from octanol to decane. A much slower loss of water-solvent and concomitant slower up-concentration of the NaCl solute resulted in a lower tendency to nucleate and slower crystal growth because much less excess material was available at the onset of nucleation in the decane system as compared to the octanol system. Thus, the crystal structure is reported to be dendritic for NaCl solution microdroplets dissolving rapidly and nucleating violently in octanol, while they are formed as single cubic crystals in a gentler way for solution-dissolution in decane. These new techniques and analyses can now also be used for any other system where all relevant parameters are known. An example of this is control of drug/hydrogel/emulsion particle size change due to solvent uptake.

An Activity-Based Dissolution Model for Solute-Containing Microdroplets.

When a solute is present in an aqueous droplet, the water activity in the droplet and the rate of droplet dissolution are both decreased (as compared to a pure water droplet). One of the main parameters that controls this effect is the dynamically changing solute concentration, and therefore water activity and chemical potential, at the droplet interface. This work addresses the importance of understanding how water activity changes during solution droplet dissolution. A model for dissolution rate is presented that accounts for the kinetic effects of changing water activity at the droplet interface during the dissolution of an aqueous salt solution microdroplet into a second immiscible liquid phase. The important underlying question in this model is whether the dissolving component can be considered in local equilibrium on both sides of the droplet interface and whether this assumption is sufficient to account for the kinetics of dissolution. The dissolution model is based on the Epstein-Plesset equation, which has previously been applied to pure gas (bubble) and liquid (droplet) dissolution into liquid phases, but not to salt solutions. The model is tested by using the micropipet technique to form and observe the dehydration of single NaCl solution microdroplets in octanol or butyl acetate. The model successfully predicts the droplet diameter as a function of time in both organic solvents. The NaCl concentration in water is measured well into the supersaturated area >5.4 M, and the supersaturation limit at which NaCl nucleation happens is reported to be 10.24 ± 0.31 M.

Hygroscopic behavior of NaCl–MgCl<sub>2</sub> mixture particles as nascent sea-spray aerosol surrogates and observation of efflorescence during humidification

Abstract. As Na+, Mg2+, and Cl− are major ionic constituents of seawater, NaCl–MgCl2 mixture particles might represent sea-spray aerosols (SSAs) better than pure NaCl. However, there have been very few hygroscopic studies of pure MgCl2 and NaCl–MgCl2 mixture aerosol particles despite the MgCl2 moiety playing a major role in the hygroscopic behavior of nascent SSAs. Laboratory-generated pure MgCl2 and NaCl–MgCl2 mixture aerosol particles with 12 mixing ratios (0.01 ≤ mole fraction of NaCl (XNaCl) ≤ 0.9) were examined systematically by optical microscopy (OM), in situ Raman micro-spectrometry (RMS), and scanning electron microscopy/energy dispersive X-ray spectrometry (SEM/EDX) elemental X-ray mapping to observe their hygroscopic behavior, derive the experimental phase diagrams, and obtain the chemical micro-structures. Dry-deposited MgCl2 ⋅ 6H2O particles exhibited a deliquescence relative humidity (DRH) of ~ 33.0 % and an efflorescence RH (ERH) of 10.8–9.1 %, whereas the nebulized pure MgCl2 and MgCl2-dominant particles of XNaCl = 0.026 (eutonic) and 0.01 showed single-stage transitions at DRH of ~ 15.9 % and ERH of 10.1–3.2 %. The characteristic OH-stretching Raman signatures indicated the crystallization of MgCl2 ⋅ 4H2O at low relative humidities (RHs), suggesting that the kinetic barrier to MgCl2 ⋅ 6H2O crystallization is not overcome in the timescale of the dehydration measurements. The NaCl–MgCl2 mixture particles of 0.05 ≤ XNaCl ≤ 0.9 generally showed two-stage deliquescence: first at the mutual DRH (MDRH) of ~ 15.9 %; and second with the complete dissolution of NaCl at the second DRHs depending on the mixing ratios, resulting in a phase diagram composed of three distinct phases. During dehydration, most particles of 0.05 ≤ XNaCl ≤ 0.9 exhibited two-stage efflorescence: first, by the homogeneous nucleation of NaCl; and second, at mutual ERH (MERH) of ~ 10.4–2.9 %, by the crystallization of the MgCl2 ⋅ 4H2O moiety, also resulting in three distinct phases. Interestingly, particles of XNaCl = 0.1 and 0.2 frequently showed three different types of mutual deliquescence behaviors. The first type exhibited an MDRH at ~ 15.9 %. The second exhibited the first MDRH at ~ 15.9 %, efflorescence to MgCl2 ⋅ 6H2O (confirmed by in situ RMS) at RH of ~ 16.1–25.0 %, and a second MDRH at ~ 33.0 %. The third showed an MDRH at ~ 33.0 %. Some particles of XNaCl = 0.1 and 0.2 also exhibited higher MERHs = 15.2–11.9 % and 23.7–15.3 %, respectively, forming MgCl2 ⋅ 6H2O. These observations suggest that the presence of sufficient condensed water and optimally sized crystalline NaCl (XNaCl = 0.1 and 0.2) acting as heterogeneous nucleation seeds helps overcome the kinetic barrier, leading to the structural growth and crystallization of MgCl2 ⋅ 6H2O. SEM/EDX elemental X-ray mapping showed that the effloresced NaCl-rich particles contain homogeneously crystallized NaCl in the center, surrounded by MgCl2 ⋅ 4H2O. The observation of an aqueous phase over a wider RH range for NaCl–MgCl2 mixture particles indicates their more probable heterogeneous chemistry compared to pure NaCl particles as a nascent SSA surrogate.

Nucleation of NaCl from Aqueous Solution: Critical Sizes, Ion-Attachment Kinetics, and Rates

Nucleation and crystal growth are important in material synthesis, climate modeling, biomineralization, and pharmaceutical formulation. Despite tremendous efforts, the mechanisms and kinetics of nucleation remain elusive to both theory and experiment. Here we investigate sodium chloride (NaCl) nucleation from supersaturated brines using seeded atomistic simulations, polymorph-specific order parameters, and elements of classical nucleation theory. We find that NaCl nucleates via the common rock salt structure. Ion desolvation-not diffusion-is identified as the limiting resistance to attachment. Two different analyses give approximately consistent attachment kinetics: diffusion along the nucleus size coordinate and reaction-diffusion analysis of approach-to-coexistence simulation data from Aragones et al. ( J. Chem. Phys. 2012, 136, 244508 ). Our simulations were performed at realistic supersaturations to enable the first direct comparison to experimental nucleation rates for this system. The computed and measured rates converge to a common upper limit at extremely high supersaturation. However, our rate predictions are between 15 and 30 orders of magnitude too fast. We comment on possible origins of the large discrepancy.

Hygroscopic properties of NaCl and NaNO<sub>3</sub> mixture particles as reacted inorganic sea-salt aerosol surrogates

Abstract. NaCl in fresh sea-salt aerosol (SSA) particles can partially or fully react with atmospheric NOx/HNO3, so internally mixed NaCl and NaNO3 aerosol particles can co-exist over a wide range of mixing ratios. Laboratory-generated, micrometer-sized NaCl and NaNO3 mixture particles at 10 mixing ratios (mole fractions of NaCl (XNaCl) = 0.1 to 0.9) were examined systematically to observe their hygroscopic behavior, derive experimental phase diagrams for deliquescence and efflorescence, and understand the efflorescence mechanism. During the humidifying process, aerosol particles with the eutonic composition (XNaCl = 0.38) showed only one phase transition at their mutual deliquescence relative humidity (MDRH) of 67.9 (±0.5)% On the other hand, particles with other mixing ratios showed two distinct deliquescence transitions; i.e., the eutonic component dissolved at MDRH, and the remainder in the solid phase dissolved completely at their DRHs depending on the mixing ratios, resulting in a phase diagram composed of four different phases, as predicted thermodynamically. During the dehydration process, NaCl-rich particles (XNaCl > 0.38) showed a two stage efflorescence transition: the first stage was purely driven by the homogeneous nucleation of NaCl and the second stage at the mutual efflorescence RH (MERH) of the eutonic components, with values in the range of 30.0–35.5%. Interestingly, aerosol particles with the eutonic composition (XNaCl = 0.38) also showed two-stage efflorescence, with NaCl crystallizing first followed by heterogeneous nucleation of the remaining NaNO3 on the NaCl seeds. NaNO3-rich particles (XNaCl ≤ 0.3) underwent single-stage efflorescence transitions at ERHs progressively lower than the MERH because of the homogeneous nucleation of NaCl and the almost simultaneous heterogeneous nucleation of NaNO3 on the NaCl seeds. SEM/EDX elemental mapping indicated that the effloresced NaCl–NaNO3 particles at all mixing ratios were composed of a homogeneously crystallized NaCl moiety in the center, surrounded either by the eutonic component (for XNaCl > 0.38) or NaNO3 (for XNaCl ≤ 0.38). During the humidifying or dehydration process, the amount of eutonic composed part drives particle/droplet growth or shrinkage at the MDRH or MERH (second ERH), respectively, and the amount of pure salts (NaCl or NaNO3 in NaCl- or NaNO3-rich particles, respectively) drives the second DRHs or first ERHs, respectively. Therefore, their behavior can be a precursor to the optical properties and direct radiative forcing for these atmospherically relevant mixture particles representing the coarse, reacted inorganic SSAs. In addition, the NaCl–NaNO3 mixture aerosol particles can maintain an aqueous phase over a wider RH range than pure NaCl particles as SSA surrogate, making their heterogeneous chemistry more probable.

Hydrogen vacancies facilitate hydrogen transport kinetics in sodium hydride nanocrystallites

We report ab initio calculations based on density-functional theory, of the vacancy-mediated hydrogen migration energy in bulk NaH and near the NaH(001) surface. The estimated rate of the vacancy mediated hydrogen transport, obtained within a hopping diffusion model, is consistent with the reaction rates of H-D exchange in nano-NaH at the relatively low temperatures observed in recent neutron studies on TiCl3-doped NaAlH4. We further obtained the formation energy for hydrogen vacancies and interstitials in NaH in all relevant charged states. These formation energies are too high to lead to the abundant hydrogen concentrations seen experimentally. Ab initio calculations on the NaCl//NaH interface are presented to provide an insight into the mechanism which may lead to high hydrogen concentrations. We show that the formation of an fcc-Na interlayer during the growth of NaH on top of NaCl is plausible, providing a source of vacancies and leading to fast hydrogen transport. The low interface energies for NaCl//NaH are consistent with an easy growth of NaH crystallites on NaCl nucleation centers, which may, therefore, act as grain refiners.

Nucleation of NaCl Nanoparticles in Supercritical Water: Molecular Dynamics Simulations

Formation of NaCl nanoparticles in supercritical water is studied using molecular dynamics simulation method. We have simulated particle nucleation and growth in NaCl-H2O fluids, with salt concentration of 5.1 wt %, in the temperature and density range of 673-1073 K and 0.17-0.34 g/cm(3), respectively. The cluster size distributions, the size of critical nuclei and cluster lifetimes are reported. The size distribution of emerging clusters shows a very strong dependence on the system's density, with larger clusters forming at lower densities. Clusters consisting of approximately 14-24 ions appear critical for the thermodynamic states examined. The local structures of critical clusters are found to be amorphous. The lifetime values for clusters containing more than 20 ions are in the range of 10-50 ps. We have calculated the NaCl nucleation rates, which appear to be on the order of 10(28) cm(-3) s(-1).

海塩エアロゾル粒子の含水状態に及ぼす海水微量成分の影響

The effects of trace components of seawater on water content of sea-salt aerosol have been investigated by infrared spectroscopy and thermal analysis. Seawater droplets of a median diameter ca 0.35μm have been formed by atomizing an artificial seawater under ambient conditions. Humidity of the sea-salt aerosol was controlled by humidifying dried sea-salt aerosol or dehumidifying the seawater droplets. As a result, it was proven that the water content of dried sea-salt aerosol was much higher than that of NaCl aerosol due to the hydration of the trace components of seawater. In addition, the crystallization point of dried sea-salt aerosol shifted to a higher humidity than that of NaCl aerosol. The reason for this is that the crystallization of CaSO4 occurs prior to the NaCl nucleation and it leads to the heterogeneous nucleation when the water content of seawater droplets decreases.

Ion-Induced Nucleationin Solution: Promotion of Solute Nucleation in Charged Levitated Droplets

We have investigated the nucleation and growth of sodium chloride in both single quiescent charged droplets and charged droplet populations that were levitated in an electrodynamic levitation trap (EDLT). In both cases, the magnitude of a droplet's net excess charge (ions(DNEC)) influenced NaCl nucleation and growth, albeit in different capacities. We have termed the phenomenon ion-induced nucleation in solution. For single quiescent levitated droplets, an increase in ions(DNEC) resulted in a significant promotion of NaCl nucleation, as determined by the number of crystals observed. For levitated droplet populations, a change in NaCl crystal habit, from regular cubic shapes to dome-shaped dendrites, was observed once a surface charge density threshold of -9 x 10(-4) e.nm(-2) was surpassed. Although promotion of NaCl nucleation was observed for droplet population experiments, this can be attributed in part to the increased rate of solvent evaporation observed for levitated droplet populations having a high net charge. Promotion of nucleation was also observed for two organic acids, 2,4,6-trihydroxyacetophenone monohydrate (THAP) and alpha-cyano-4-hydroxycinnamic acid (CHCA). These results are of direct relevance to processes that occur in both soft-ionization techniques for mass spectrometry and to a variety of industrial processes. To this end, we have demonstrated the use of ion-induced nucleation in solution to form ammonium nitrate particles from levitated droplets to be used in in vitro toxicology studies of ambient particle types.

Atomistic nature of NaCl nucleation at the solid-liquid interface

The early stage of heterogeneous nucleation of NaCl from supersaturated NaCl aqueous solution at the water-NaCl (001) interface has been investigated by molecular dynamics simulations. The critical size of the nuclei for spontaneous growth was found to be as small as two atoms (a Na(+)-Cl(-) ion pair) at high supersaturation. Due to the presence of a relatively stable water network and the effect of the hydration force at the interface, the stable nuclei formed on the NaCl (001) are found to contain more Na(+) ions than Cl(-) ions. The different deposition characteristics of the Na(+) and Cl(-) solutes lead to a positively charged substrate and thus may introduce another driving force for nucleation besides the level of solution supersaturation. The role of water was further confirmed by comparison with NaCl epitaxy growth in the vacuum.