A New Monte Carlo Method for Direct Calculation of the Critical Size and the Formation Work of a Microdrop

Шевкунов, С. В.; Vorontsov-Vèlyaminov, P. N.; Martsinovski, A. A.

doi:10.1080/08927029008022126

Cited by 61 publications

(18 citation statements)

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“…The partition function and the method of sampling in this ensemble have been presented elsewhere. 43 In the current work the hydration structure of clusters with sizes in the nϭ1 -15 range and at Tϭ297 K have been examined. To avoid evaporation, the clusters remained confined in a spherical cavity with perfectly reflective walls of approximately 10 Å in radius.…”

Section: ͑1͒mentioning

confidence: 99%

Hydration shell structure of the OH−(H2O)n=1–15 clusters from a model potential energy function

Vegiri

Шевкунов

2000

The Journal of Chemical Physics

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The structural properties of the hydrated hydroxide ion are studied in terms of a many-body potential energy function that has been parameterized according to the experimentally determined ͓Arshadi et al., J. Phys. Chem. 74, 1475, 1483 ͑1970͔͒ enthalpy and entropy changes for the first five association reactions of the ion with H 2 O. Clusters in the nϭ1 -15 size range are examined through a canonical Monte Carlo simulation at Tϭ297 K. The resultant structures, irrespective of the cluster size, are predominantly linear of the dendrite type, with the first shell consisting of two water molecules. Minimum energy structures at Tϭ0 K for nϭ2 and 3 compare well with ab initio conformations.

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Section: ͑1͒mentioning

confidence: 99%

Hydration shell structure of the OH−(H2O)n=1–15 clusters from a model potential energy function

Vegiri

Шевкунов

2000

The Journal of Chemical Physics

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“…In such cases, other more sophisticated methods to determine the chemical potentials, such as gradual insertion in extended ensembles [24,25,26], can be applied alternatively.…”

Section: Introductionmentioning

confidence: 99%

Grand Equilibrium: vapour-liquid equilibria by a new molecular simulation method

2002

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A new molecular simulation method for the calculation of vapour-liquid equilibria of mixtures is presented. In this method, the independent thermodynamic variables are temperature and liquid composition. In the first step, one isobaric isothermal simulation for the liquid phase is performed, in which the chemical potentials of all components and their derivatives with respect to the pressure, i.e., the partial molar volumes, are calculated. From these results, first order Taylor series expansions for the chemical potentials as functions of the pressure µ i (p) at constant liquid composition are determined. That information is needed, as the specified pressure in the liquid will generally not be equal to the equilibrium pressure, which has to be found in the course of a vapour simulation.In the second step, one pseudo grand canonical simulation for the vapour phase is per-

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“…The resulting values are presented in the table. The free energy was calculated in a bicanonical statistical ensemble by a method developed in [34,35]. Numerical values of the interaction parameters were determined by the method of successive approximations.…”

Section: Simulation Of the Cluster H 3 O + (H 2 O) Nmentioning

confidence: 99%

Computer simulation of molecular complexes H3O+(H2O)n under conditions of thermal fluctuations: I. Interactions in the system

Шевкунов

2004

Russ J Gen Chem

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The simplest pair model of intermolecular interactions fails to reproduce known experimental free energy and entropy of hydration of H 3 O + ions in water vapor. A fit to experiment is attained only when covalent bonds and nonpair interactions, which are of particular importance at contact distances from the ion, are taken into account. An interaction model was constructed, which allows the experimental free energies of cluster formation to be reproduced to fractions of k B T by the Monte3Carlo method. Numerical values of interaction parameters were obtained by fitting simulated results to refined experimental data. Problem of description of interactions in ion3water clusters. Though the boundary between clusters and molecules is rather conventional, it is a common practice to associate formation of molecules with formation of chemical bonds. A distinctive feature of such interactions is their nonpair nature whose extreme manifestation is the effect of saturation of chemical bonds according to atomic valence. The nature of interactions (pair or nonpair) might serve as a criterion in attributing a certain molecular complex to clusters or molecules. However, this scheme, too, has its disadvantages. Nonpair interactions also can be of essential importance in typical clusters, especially in clusters formed in a strong electric field of an ion. Quantum-chemical calculations of the energies of various molecular configurations were fulfilled by Kistenmacher et al. [1] for clusters with 2310 water molecules on the Li + , Na + , K + , F 3 , and Cl 3 ions. The numerical results were approximated by analytic functions that were then used in statistical calculations at finite temperature. The nonpair interaction is most contributed by water3ion3water terms. Water3water3 water interactions are negligibly small. Three-body interactions make up~10% of the energy of a system (tens k B T, where k B is Boltzmann constant and T is absolute temperature), and four-body interactions make up 132%. The contributions from many-body interactions are approximately proportional to the amount of water3ion3water triplets in the first coordination shell. Interactions with the ion contribute most to cluster energy.There are two basic techniques for constructing model intermolecular potentials: quantum-chemical calculations by the Hartree3Fock self-consistent field (SCF) method with subsequent corrections for electron correlations and a reconstruction of the potential from measurable thermal and structural properties of real substances. Inclusion of nonpair interactions involves multiple solution of the Schroedinger equation for a great number of molecular configurations followed by approximation of the numerical results by multidimensional functional relationships. Sequential fulfillment of this program requires huge computing expenditures. Systematic investigations aimed at the reconstruction of intermolecular potentials from thermal and structural properties of water had been initiated in early 1970s [2310]. A series of models of intermolecul...

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A New Monte Carlo Method for Direct Calculation of the Critical Size and the Formation Work of a Microdrop

Cited by 61 publications

References 3 publications

Hydration shell structure of the OH−(H2O)n=1–15 clusters from a model potential energy function

Hydration shell structure of the OH−(H2O)n=1–15 clusters from a model potential energy function

Grand Equilibrium: vapour-liquid equilibria by a new molecular simulation method

Computer simulation of molecular complexes H3O+(H2O)n under conditions of thermal fluctuations: I. Interactions in the system

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