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Title: Electrolyte pore/solution partitioning by expanded grand canonical ensemble Monte Carlo simulation

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Publication Date:
Sponsoring Org.:
OSTI Identifier:
Grant/Contract Number:
SC 0004406
Resource Type:
Journal Article: Publisher's Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 142; Journal Issue: 12; Related Information: CHORUS Timestamp: 2017-06-23 04:11:08; Journal ID: ISSN 0021-9606
American Institute of Physics
Country of Publication:
United States

Citation Formats

Moucka, Filip, Bratko, Dusan, and Luzar, Alenka. Electrolyte pore/solution partitioning by expanded grand canonical ensemble Monte Carlo simulation. United States: N. p., 2015. Web. doi:10.1063/1.4914461.
Moucka, Filip, Bratko, Dusan, & Luzar, Alenka. Electrolyte pore/solution partitioning by expanded grand canonical ensemble Monte Carlo simulation. United States. doi:10.1063/1.4914461.
Moucka, Filip, Bratko, Dusan, and Luzar, Alenka. 2015. "Electrolyte pore/solution partitioning by expanded grand canonical ensemble Monte Carlo simulation". United States. doi:10.1063/1.4914461.
title = {Electrolyte pore/solution partitioning by expanded grand canonical ensemble Monte Carlo simulation},
author = {Moucka, Filip and Bratko, Dusan and Luzar, Alenka},
abstractNote = {},
doi = {10.1063/1.4914461},
journal = {Journal of Chemical Physics},
number = 12,
volume = 142,
place = {United States},
year = 2015,
month = 3

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record at 10.1063/1.4914461

Citation Metrics:
Cited by: 9works
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  • Using a newly developed grand canonical Monte Carlo approach based on fractional exchanges of dissolved ions and water molecules, we studied equilibrium partitioning of both components between laterally extended apolar confinements and surrounding electrolyte solution. Accurate calculations of the Hamiltonian and tensorial pressure components at anisotropic conditions in the pore required the development of a novel algorithm for a self-consistent correction of nonelectrostatic cut-off effects. At pore widths above the kinetic threshold to capillary evaporation, the molality of the salt inside the confinement grows in parallel with that of the bulk phase, but presents a nonuniform width-dependence, being depleted atmore » some and elevated at other separations. The presence of the salt enhances the layered structure in the slit and lengthens the range of inter-wall pressure exerted by the metastable liquid. Solvation pressure becomes increasingly repulsive with growing salt molality in the surrounding bath. Depending on the sign of the excess molality in the pore, the wetting free energy of pore walls is either increased or decreased by the presence of the salt. Because of simultaneous rise in the solution surface tension, which increases the free-energy cost of vapor nucleation, the rise in the apparent hydrophobicity of the walls has not been shown to enhance the volatility of the metastable liquid in the pores.« less
  • In this article the Taylor-expansion method is introduced by which Monte Carlo (MC) simulations in the canonical ensemble can be speeded up significantly, Substantial gains in computational speed of 20-40% over conventional implementations of the MC technique are obtained over a wide range of densities in homogeneous bulk phases. The basic philosophy behind the Taylor-expansion method is a division of the neighborhood of each atom (or molecule) into three different spatial zones. Interactions between atoms belonging to each zone are treated at different levels of computational sophistication. For example, only interactions between atoms belonging to the primary zone immediately surroundingmore » an atom are treated explicitly before and after displacement. The change in the configurational energy contribution from secondary-zone interactions is obtained from the first-order term of a Taylor expansion of the configurational energy in terms of the displacement vector d. Interactions with atoms in the tertiary zone adjacent to the secondary zone are neglected throughout. The Taylor-expansion method is not restricted to the canonical ensemble but may be employed to enhance computational efficiency of MC simulations in other ensembles as well. This is demonstrated for grand canonical ensemble MC simulations of an inhomogeneous fluid which can be performed essentially on a modern personal computer.« less
  • Coexistence curves of square-well fluids with variable interaction width and of the restricted primitive model for ionic solutions have been investigated by means of grand canonical Monte Carlo simulations aided by histogram reweighting and multicanonical sampling techniques. It is demonstrated that this approach results in efficient data collection. The shape of the coexistence curve of the square-well fluid with short potential range is nearly cubic. In contrast, for a system with a longer potential range, the coexistence curve closely resembles a parabola, except near the critical point. The critical compressibility factor for the square-well fluids increases with increasing range. Themore » critical behavior of the restricted primitive model was found to be consistent with the Ising universality class. The critical temperature was obtained as T{sub c}=0.0490{plus_minus}0.0003 and the critical density {rho}{sub c}=0.070{plus_minus}0.005, both in reduced units. The critical temperature estimate is consistent with the recent calculation of Caillol {ital et al.} [J. Chem. Phys. {bold 107}, 1565 (1997)] on a hypersphere, while the critical density is slightly lower. Other previous simulations have overestimated the critical temperature of this ionic fluid due to their failure to account for finite-size effects in the critical region. The critical compressibility factor (Z{sub c}=P{sub c}/{rho}{sub c}T{sub c}) for the ionic fluid was obtained as Z{sub c}=0.024{plus_minus}0.004, an order of magnitude lower than for nonionic fluids. {copyright} {ital 1999 American Institute of Physics.}« less
  • A model of triangulated random surfaces which is the discrete analog of the Polyakov string is considered. An algorithm is proposed which enables one to study the model by the Monte Carlo method in the grand canonical ensemble. Preliminary results on the determination of the critical index ..gamma.. are presented.
  • A quantum Monte Carlo method with a nonlocal update scheme is presented. The method is based on a path-integral decomposition and a worm operator which is local in imaginary time. It generates states with a fixed number of particles and respects other exact symmetries. Observables like the equal-time Green's function can be evaluated in an efficient way. To demonstrate the versatility of the method, results for the one-dimensional Bose-Hubbard model and a nuclear pairing model are presented. Within the context of the Bose-Hubbard model the efficiency of the algorithm is discussed.