Miraslau L. Barabash

We use all-atom molecular dynamics simulations to investigate ionic conduction in a short, charged, single-wall carbon nanotube. They reveal ionic Coulomb blockade (ICB) oscillations in the current as a function of the fixed charge on the wall, and an associated occupancy staircase. Current peaks related to fluctuations around the 2 → 1 and 1 → 0 steps in occupancy are clearly resolved, in agreement with ICB theory. Current peaks were also observed at constant occupancy. These unpredicted secondary peaks are attributed to edge effects involving a remote knock-on mechanism; they are attenuated, or absent, for certain choices of model parameters. The key parameters of the system that underlie the current oscillations are estimated using ICB theory and the potential of the mean force. Future perspectives opened up by these observations are discussed.

In order to permeate a nanopore, an ion must overcome a dehydration energy barrier caused by the redistribution of surrounding water molecules. The redistribution is inhomogeneous, anisotropic and strongly position-dependent, resulting in complex patterns that are routinely observed in molecular dynamics simulations. Here, we study the physical origin of these patterns and of how they can be predicted and controlled. We introduce an analytic model able to predict the patterns in a graphene nanopore in terms of experimentally accessible radial distribution functions, giving results that agree well with molecular dynamics simulations. The patterns are attributable to a complex interplay of ionic hydration shells with water layers adjacent to the graphene membrane and with the hydration cloud of the nanopore rim atoms, and we discuss ways of controlling them. Our findings pave the way to designing required transport properties into nanoionic devices by optimising the structure of the hydration patterns.

In order to permeate a nanopore, an ion must overcome a dehydration energy barrier caused by the redistribution of surrounding water molecules. The redistribution is inhomogeneous, anisotropic and strongly position-dependent, resulting in complex patterns that are routinely observed in molecular dynamics simulations. We now address the questions of the physical origin of these patterns and of how they can be predicted and controlled. We introduce an analytic model able to predict the patterns in terms of experimentally accessible radial distributions functions, yielding results that agree well with molecular dynamics simulations. We show that the patterns are attributable to a complex interplay of ionic hydration shells with water layers adjacent to the membrane and with the hydration cloud of the nanopore rim atoms, and we discuss ways of controlling them. Our findings pave the way to designing required transport properties into nanoionic devices by optimising the structure of the hydration patterns.

Selective permeation through graphene nanopores is attracting increasing interest as an efficient and cost-effective technique for water desalination and purification. In this work, using umbrella sampling and molecular dynamics simulations with constant electric field, we analyze the influence of pore charge on potassium and chloride ion permeation. As pore charge is increased, the barrier of the potential of mean force (PMF) gradually decreases until it turns into a well split in two subminima. While in the case of K⁺ this pattern can be explained as an increasing electrostatic compensation of the desolvation cost, in the case of Cl⁻ the pattern can be attributed to the accumulation of a concentration polarization layer of potassium ions screening pore charge. The analysis of potassium PMFs in terms of forces revealed a conflicting influence on permeation of van der Waals and electrostatic forces that both undergo an inversion of their direction as pore charge is increased. Even if the most important transition involves the interplay between the electrostatic forces exerted by graphene and water, the simulations also revealed an important role of the changing distribution of potassium and chloride ions. The influence of pore charge on the orientation of water molecules was also found to affect the van der Waals forces they exert on potassium.

We consider the selective permeation of ions through narrow water-filled channels in the presence of strong interaction between the ions. These interactions lead to highly correlated ionic motion, which can conveniently be described via the concept of a quasiparticle. Here, we connect the quasiparticle’s effective potential and the multi-ion potential of the mean force, found through molecular dynamics simulations, and we validate the method on an analytical toy model of the KcsA channel. Possible future applications of the method to the connection between molecular dynamical calculations and the experimentally measured current-voltage and current-concentration characteristics of the channel are discussed.

The problem of predicting selective transport of ions through nano-pores from their structure in the biological and nano-technological systems is addressed. We use a molecular dynamics simulation to provide insight into the key physical parameters of nano-pores and develop a self-consistent analytic theory describing ionic conduction and selectivity through these devices. We analyse the ion's dehydration and excess chemical potential, derive an expression for the conductivity of the nano-pore, and emphasize the role of fluctuations in its performance. The theory is verified by comparison of the predicted current-voltage characteristics with the molecular dynamics results and experimental data obtained for a graphene nano-pore and the KcsA biological channel.