Ideal Conductor Model: An Analytical Finite-Size Correction for Nonequilibrium Molecular Dynamics Simulations of Ion Transport through Nanoporous Membranes. 2022

Brian A Shoemaker, and Tiago S Domingues, and Amir Haji-Akbari
Department of Chemical and Environmental Engineering, Yale University, New Haven, Connecticut06520, United States.

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.

UI MeSH Term Description Entries
D007473 Ion Channels Gated, ion-selective glycoproteins that traverse membranes. The stimulus for ION CHANNEL GATING can be due to a variety of stimuli such as LIGANDS, a TRANSMEMBRANE POTENTIAL DIFFERENCE, mechanical deformation or through INTRACELLULAR SIGNALING PEPTIDES AND PROTEINS. Membrane Channels,Ion Channel,Ionic Channel,Ionic Channels,Membrane Channel,Channel, Ion,Channel, Ionic,Channel, Membrane,Channels, Ion,Channels, Ionic,Channels, Membrane
D007700 Kinetics The rate dynamics in chemical or physical systems.
D013816 Thermodynamics A rigorously mathematical analysis of energy relationships (heat, work, temperature, and equilibrium). It describes systems whose states are determined by thermal parameters, such as temperature, in addition to mechanical and electromagnetic parameters. (From Hawley's Condensed Chemical Dictionary, 12th ed) Thermodynamic
D017136 Ion Transport The movement of ions across energy-transducing cell membranes. Transport can be active, passive or facilitated. Ions may travel by themselves (uniport), or as a group of two or more ions in the same (symport) or opposite (antiport) directions. Antiport,Ion Cotransport,Ion Exchange, Intracellular,Symport,Uniport,Active Ion Transport,Facilitated Ion Transport,Passive Ion Transport,Cotransport, Ion,Exchange, Intracellular Ion,Intracellular Ion Exchange,Ion Transport, Active,Ion Transport, Facilitated,Ion Transport, Passive,Transport, Active Ion,Transport, Ion
D056004 Molecular Dynamics Simulation A computer simulation developed to study the motion of molecules over a period of time. Molecular Dynamics Simulations,Molecular Dynamics,Dynamic, Molecular,Dynamics Simulation, Molecular,Dynamics Simulations, Molecular,Dynamics, Molecular,Molecular Dynamic,Simulation, Molecular Dynamics,Simulations, Molecular Dynamics

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