Boundary-Monte Carlo Method for Neutral and Charged Confined Fluids

Summary, in English

In this work, we describe a new Monte Carlo (MC) simulation method to investigate highly coupled fluids in confined geometries at a constant chemical potential. This method is based on so-called multi-scale Hamiltonian methods, wherein the chemical potential is determined using a more amenable Hamiltonian for a fluid in an "outer"region, which facilitates standard methods, such as grand canonical MC simulations or Widom's particle insertion method. The (inner region) fluid of interest is placed in diffusive contact with the simpler outer fluid via a boundary zone wherein the Hamiltonian is transformed. The current method utilizes an ideal fluid for the outer regions, which allows for implicit rather than explicit simulations. Only the boundary and inner region need explicit consideration; hence, the nomenclature used is boundary-Monte Carlo. We illustrate the utility of the method for simple neutral and charged fluids in cylindrical and planar pores. In the latter case, we use a dense room-temperature ionic liquid model and illustrate how the boundary zone establishes a proper Donnan equilibrium between inner and outer fluids in the presence of charged planar electrodes. Thus, the method allows direct calculation of properties such as the differential capacitance, without the need for additional difficult calculations of the requisite Donnan potential.

• Author: Phuong Vo; Jan Forsman; Clifford E. Woodward
• Department/s: Computational Chemistry
• Publishing year: 2022-06-14
• Language: English
• Pages: 3766-3780
• Publication/Series: Journal of Chemical Theory and Computation
• Volume: 18
• Issue: 6
• Links: http://dx.doi.org/10.1021/acs.jctc.1c01146
• Document type: Journal article
• Publisher: The American Chemical Society (ACS)
• Topic: Fluid Mechanics
• Status: Published
• ISBN/ISSN/Other: ISSN: 1549-9618