A new type of instability -electrokinetic instability -and an unusual transition to chaotic motion near a chargeselective surface (semi-selective electric membrane, electrode or system of micro-/nanochannels) was studied by numerical integration of the Nernst-Planck-Poisson-Stokes system and a weakly nonlinear analysis near the threshold of instability. A special finite-difference method was used for the space discretization along with a semi-implicit 3 1 3 -step Runge-Kutta scheme for the integration in time. The linear stability problem was resolved by a spectral method.Two kinds of initial conditions were considered: (a) white noise initial conditions to mimic "room disturbances" and subsequent natural evolution of the solution; (b) an artificial monochromatic ion distribution with a fixed wave number to simulate regular wave patterns. The results were studied from the viewpoint of hydrodynamic stability and bifurcation theory. The threshold of electroconvective movement was found by the linear spectral stability theory, the results of which were confirmed by numerical simulation of the entire system. The following regimes, which replace each other as the potential drop between the selective surfaces increases, were obtained: one-dimensional steady solution; two-dimensional steady electroconvective vortices (stationary point in a proper phase space); unsteady vortices aperiodically changing their parameters (homoclinic contour); periodic motion (limit cycle); and chaotic motion.The transition to chaotic motion did not include Hopf bifurcation. Numerical resolution of the thin concentration polarization layer showed spike-like charge profiles along the surface, which could be, depending on the regime, either steady or aperiodically coalescent.The numerical investigation confirmed the experimentally observed absence of regular (near-sinusoidal) oscillations for the overlimiting regimes. There is a qualitative agreement of the experimental and the theoretical values of the threshold of instability, the dominant size of the observed coherent structures, and the experimental and theoretical volt-current characteristics.

In the present work, four nontrivial stages of electrokinetic instability are identified by direct numerical simulation (DNS) of the full Nernst-Planck-Poisson-Stokes system: (i) a stage of the influence of the initial conditions (milliseconds); (ii) one-dimensional (1D) self-similar evolution (milliseconds-seconds); (iii) a primary instability of the self-similar solution (seconds); (iv) a nonlinear stage with secondary instabilities. The self-similar character of evolution at moderately large times is confirmed. Rubinstein and Zaltzman instability and noise-driven nonlinear evolution toward overlimiting regimes in ion-exchange membranes are numerically simulated and compared with theoretical and experimental predictions. The primary instability which happens during this stage is found to arrest a self-similar growth of the diffusion layer. It also specifies its characteristic length as was first experimentally predicted by Yossifon and Chang [G. Yossifon and H.-C. Chang, Phys. Rev. Lett. 101, 254501 (2008)]. A novel principle for the characteristic wave-number selection from the broadband initial noise is established.

A direct numerical simulation of the three-dimensional elektrokinetic instability near a charge-selective surface (electric membrane, electrode, or system of micro- or nanochannels) has been carried out and analyzed. A special finite-difference method has been used for the space discretization along with a semi-implicit 31/3-step Runge-Kutta scheme for the integration in time. The calculations employ parallel computing. Three characteristic patterns, which correspond to the overlimiting currents, are observed: (a) two-dimensional electroconvective rolls, (b) three-dimensional regular hexagonal structures, and (c) three-dimensional structures of spatiotemporal chaos, which are a combination of unsteady hexagons, quadrangles, and triangles. The transition from (b) to (c) is accompanied by the generation of interacting two-dimensional solitary pulses.

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