Sampling mobility profiles of confined fluids with equilibrium molecular dynamics simulations

Abstract

We show how to evaluate mobility profiles, characterizing the transport of confined fluids under a perturbation, from equilibrium molecular simulations. The correlation functions derived with the Green-Kubo formalism are difficult to sample accurately and we consider two complementary strategies: improving the spacial sampling thanks to a new estimator of the local fluxes involving the forces acting on the particles in addition to their positions and velocities, and improving temporal sampling thanks to the Einstein-Helfand approach instead of the Green-Kubo one. We illustrate this method on the case of a binary mixture confined between parallel walls, under a pressure or chemical potential gradient. All equilibrium methods are compared to standard non-equilibrium molecular dynamics (NEMD) and provide the correct mobility profiles. We recover quantitatively fluid viscosity and diffusio-osmostic mobility in the bulk part of the pore. Interestingly, the matrix of mobility profiles for local fluxes is not symmetric, unlike the Onsager matrix for the total fluxes. Even the most computationally efficient equilibrium method (Einstein-Helfand combined with the force-based estimator) remains less efficient than NEMD to determine a single mobility profile. However, the equilibrium approach provides all responses to all perturbations simultaneously, whereas NEMD requires the simulation of several types of perturbations to determine the various responses, each with different magnitudes to check the validity of the linear regime. While NEMD seems more competitive for the present example, the balance should be different for more complex systems, in particular for electrolyte solutions for the responses to pressure, salt concentration and electric potential gradients.

References in corpus (22)

• Nanofluidics, from bulk to interfaces
• Osmosis, from molecular insights to large-scale applications
• Molecular streaming and its voltage control in ångström scale channels
• Liquid friction on charged surfaces: from hydrodynamic slippage to electrokinetics
• Zero-variance principle for Monte Carlo algorithms
• What controls thermo-osmosis? Molecular simulations show the critical role of interfacial hydrodynamics
• Molecular Simulation of Thermo-osmotic slip
• Accurate thermal conductivities from optimally short molecular dynamics simulations
• Molecular dynamics simulation of electrokinetic flow of an aqueous electrolyte solution in nanochannels
• Osmotic and diffusio-osmotic flow generation at high solute concentration. I. Mechanical approaches
• Transport and Helfand moments in the Lennard-Jones fluid. I. Shear viscosity
• Osmotic and diffusio-osmotic flow generation at high solute concentration. II. Molecular dynamics simulations
• Better than counting: Density profiles from force sampling
• Giant thermoelectric response of nanofluidic systems driven by water excess enthalpy
• On the effect of the thermostat in non-equilibrium molecular dynamics simulations
• Zero-variance zero-bias quantum Monte Carlo estimators of the spherically and system-averaged pair density
• Efficient Monte Carlo Calculations of the One-Body Density
• Heat transport in insulators from ab initio Green-Kubo theory
• Pressure Gradients Fail to Predict Diffusio-Osmosis
• Computing three-dimensional densities from force densities improves statistical efficiency
• Comparing Theory and Simulation for Thermo-osmosis
• Generic transport coefficients of a confined electrolyte solution

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• Intrinsic interface adsorption drives selectivity in atomically smooth nanofluidic channels