Ideal Conductor Model: An Analytical Finite-Size Correction for Nonequilibrium Molecular Dynamics Simulations of Ion Transport through Nanoporous Membranes

BA Shoemaker and TS Domingues and A Haji-Akbari, JOURNAL OF CHEMICAL THEORY AND COMPUTATION, 18, 7142-7154 (2022).

DOI: 10.1021/acs.jctc.2c00375

Modulating ion transport through nanoporous membranes is critical to many important chemical and biological separation processes. The corresponding transport timescales, however, are often too long to capture accurately using conventional molecular dynamics (MD). Recently, path sampling techniques, such as forward-flux sampling (FFS), have emerged as attractive alternatives for efficiently and accurately estimating arbitrarily long ionic passage times. Here, we use non- equilibrium MD and FFS to explore how the kinetics and mechanisms of pressure-driven chloride transport through a nanoporous graphitic membrane are affected by its lateral dimensions. We not only find ionic passage times and free energy barriers to decrease dramatically upon increasing the membrane surface area but also observe an abrupt and discontinuous change in the locus of the transition state. These strong finite size effects arise due to the cumulative effect of the periodic images of the leading ion entering the pore on the distribution of the induced excess charge at the membrane surface in the feed. By assuming that the feed is an ideal conductor, we analytically derive a finite size correction term that can be computed from the information obtained from a single simulation and successfully use it to obtain corrected free energy profiles with no dependence on the system size. We then estimate ionic passage times in the thermodynamic limit by assuming an Eyring-type dependence of rates on barriers with a size-independent prefactor. This approach constitutes a universal framework for removing finite size artifacts in molecular simulations of ion transport through nanoporous membranes and biological channel proteins.

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