Structure and Dynamics of the Aqueous Liquid−Vapor Interface:  A Comprehensive Particle-Based Simulation Study

Kuo, I‐Feng W.; Mundy, Christopher J.; Eggimann, Becky L.; McGrath, Matthew J.; Siepmann, J. Ilja; Chen, Bin; Vieceli, and John; Tobias, Douglas J.

doi:10.1021/jp056330t

Cited by 125 publications

(228 citation statements)

References 72 publications

(193 reference statements)

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“…The PDM-H2O is a simple isotropic model which is able to reproduce with a small error the electrostatic properties of chloride-water dimers. 24 Nevertheless, as for other models used in the previous studies, 30,31 when it is transferred to condensed phase, it does not perform so well since the water dipole moment is underestimated by ϳ25%. On the other hand, the PD2-H2O model performs fairly well, showing a small shift of ϳ0.2 D with respect to the ab initio curve.…”

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confidence: 77%

“…For example, given that the surface propensity of the chloride ion ͑and of the bigger halogenide anions͒ is explained as a minimum in the free energy at the surface due to ion polarization, 3 an exact modeling of polarizable interactions would provide more accurate quantitative estimates of the phenomenon. In the Introduction, it was pointed out that the solvent polarization also plays an important role; nevertheless, in some recent studies, 30,31 it was found that water molecules are underpolarized as compared to Car-Parrinello simulations. This is clearly shown in Fig.…”

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confidence: 99%

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Ab initio based polarizable force field parametrization

Masia

2008

The Journal of Chemical Physics

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Experimental and simulation studies of anion-water systems have pointed out the importance of molecular polarization for many phenomena ranging from hydrogen-bond dynamics to water interfaces structure. The study of such systems at molecular level is usually made with classical molecular dynamics simulations. Structural and dynamical features are deeply influenced by molecular and ionic polarizability, which parametrization in classical force field has been an object of long-standing efforts. Although when classical models are compared to ab initio calculations at condensed phase, it is found that the water dipole moments are underestimated by ϳ30%, while the anion shows an overpolarization at short distances. A model for chloride-water polarizable interaction is parametrized here, making use of Car-Parrinello simulations at condensed phase. The results hint to an innovative approach in polarizable force fields development, based on ab initio simulations, which do not suffer for the mentioned drawbacks. The method is general and can be applied to the modeling of different systems ranging from biomolecular to solid state simulations.

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confidence: 77%

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confidence: 99%

Ab initio based polarizable force field parametrization

Masia

2008

The Journal of Chemical Physics

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“…Molecular dynamics simulations provide quantitative predictions of ion concentrations at the surface and of the distributions of ions with depth, although the results depend on the interaction potentials used (11,34). Surface spectroscopy measurements provide important experimental validation of inorganic ion partitioning but have not yielded surface concentrations because it is not feasible to determine the depth being probed (6,8,9,14).…”

Section: Discussionmentioning

confidence: 99%

Partitioning of atmospherically relevant ions between bulk water and the water/vapor interface

Pegram

Record²

2006

Proc. Natl. Acad. Sci. U.S.A.

162

230

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Recently, surface-sensitive spectroscopy data and molecular dynamics simulations have generated intense interest in the distribution of electrolyte ions between bulk water and the air͞water interface. A partitioning model for cations and anions developed for biopolymer surface is extended here to interpret the effects of selected acids, bases, and salts on the surface tension of water. Data for electrolytes were analyzed by using a lower-bound value for the number of water molecules in the surface region [0.2 H 2O Å ؊2 (approximately two layers of water)], obtained by assuming that both Na ؉ and SO 4 2؊ (i.e., Na2SO4) are fully excluded from this region. Surface-bulk partition coefficients of atmospherically relevant anions and the proton are determined. Notably, we find that H ؉ is most strongly surface-accumulated, I ؊ is modestly accumulated, NO 3 ؊ is evenly distributed, and OH ؊ is weakly excluded.surface tension ͉ surface-bulk partition coefficients ͉ inorganic salt ions T he distribution of ions between bulk water and water located at a surface has major implications for processes in biochemistry, atmospheric chemistry, and technology. As early as 1957, the observation of negative surface potentials for aqueous solutions of alkali metal salts of I Ϫ , ClO 4 Ϫ , SCN Ϫ , and PF 6 Ϫ led to the proposal that these anions (but not the cations) were present in the interfacial region of aqueous salt solutions (1, 2). However, the traditional proposal of an ion-free water layer on the surface of salt solutions, based on their positive surface tension increments (d␥͞dm 2 Ͼ 0), went relatively unchallenged until a decade ago, when Hu and coworkers observed that the kinetics of halogen uptake by NaBr and NaI solutions were too rapid to be explained by a simple bulk-phase reaction mechanism (3). The authors concluded that significant concentrations of bromide and iodide must be present in the surface layer, even at low bulk salt concentrations. Since then, considerable attention has been focused on this topic because of its implications for atmospheric chemistry (4, 5). Surface-sensitive spectroscopic experiments (6-9), molecular dynamics simulations (10-12), and various theoretical͞experimental collaborations (13-15) provide evidence, recently reviewed (16), that, although ''hard'' and multiply charged ions are excluded from the surface, large polarizable anions (e.g., SCN Ϫ and I Ϫ ) and the proton accumulate there, in some cases at concentrations greater than in the bulk solution. Only when both ions are hard and͞or multiply charged (e.g., NaF and Na 2 SO 4 ) do the simulations show both ions excluded from the surface, in agreement with the classical picture of a salt-free layer. In other cases, almost complete cationic exclusion and various degrees of anionic accumulation at the surface result in a range of net ion depletion at the surface (13); for these cases, a correspondingly wide range of positive surface tension increments have been reported (17). We apply a recently developed two-state, single-ion partitio...

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“…61 For example, Kuo et al 62 used tan-hyperbolic function to fit the density profiles for various water models. On the other hand, Sides et al 63 and Ismail et al 64 used both tan-hyperbolic and error function for the Lennard-Jones fluid and various water models, respectively, and obtained the interfacial width.…”

Section: B Vapor-liquid Interfacial Tension Under Confinementmentioning

confidence: 99%

Vapor-liquid critical and interfacial properties of square-well fluids in slit pores

Jana

Singh

Kwak

2009

The Journal of Chemical Physics

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Computer simulation studies of a square-well fluid in a slit pore. Spreading pressure and vapor-liquid phase equilibria using the virtual-parameter-variation method J. Chem. Phys. 112, 5168 (2000) Vapor-liquid phase equilibria of square-well ͑SW͒ fluids of variable interaction range: = 1.25, 1.75, 2.0, and 3.0 in hard slit pores are studied by means of grand-canonical transition-matrix Monte Carlo ͑GC-TMMC͒ simulation. Critical density under confinement shows an oscillatory behavior as slit width, H, reduced from 12 to 1 . Two linear regimes are found for the shift in the critical temperature with the inverse in the slit width. The first regime is seen for H Ͼ 2.0 with linear increase in the slope of shift in the critical temperature against inverse slit width with increasing interaction range. Subsequent decrease in H has little consequence on the critical temperature and it remains almost constant. Vapor-liquid surface tensions of SW fluids of variable well extent in a planar slit pore of variable slit width are also reported. GC-TMMC results are compared with that from slab based canonical Monte Carlo and molecular dynamics techniques and found to be in good agreement. Although, vapor-liquid surface tension under confinement is found to be lower than the bulk surface tension, the behavior of surface tension as a function of temperature is invariant with the variable pore size. Interfacial width, , calculated using a hyperbolic function increases with decreasing slit width at a given temperature, which is contrary to what is being observed recently for cylindrical pores. Inverse scaled interfacial width ͑ / H͒, however, linearly increases with increase in the scaled temperature ͑T c,bulk − T͒ / T c,bulk .

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Structure and Dynamics of the Aqueous Liquid−Vapor Interface: A Comprehensive Particle-Based Simulation Study

Cited by 125 publications

References 72 publications

Ab initio based polarizable force field parametrization

Ab initio based polarizable force field parametrization

Partitioning of atmospherically relevant ions between bulk water and the water/vapor interface

Vapor-liquid critical and interfacial properties of square-well fluids in slit pores

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