Non-equilibrium molecular dynamics simulation study of the frequency dependent conductivity of a primitive model electrolyte in a nanopore

Abstract

The frequency dependence of electrical conductivity in a 0.1 molar univalent restricted primitive model electrolyte confined in cylindrical pores is studied by non-equilibrium molecular dynamics simulations. At high frequencies, conductivity is independent of pore size and approaches the zero value limit. The phase lag is independent of pore size and approaches the value π/2 at high frequency. At low frequencies, the conductivity is relatively constant and approaches the zero frequency (dc) conductivity value. For pores with radius smaller than 3 times the ion diameter, severe confinement effects lead to different low frequency behaviour. In these very small pores, axial collisions increase at low frequency and lead to much lower conductivity and a negative phase shift. The current response in severely confined electrolytes can be analogous to an LRC circuit with resonance at a characteristic frequency.