Proton transfer and the diffusion of H+ and OH- ions along water wires

Hydrogen and hydroxide ion transport in narrow carbon nanotubes (CNTs) of diameter 8.1 angstrom and lengths up to 582 angstrom are investigated by molecular dynamics simulations using a dissociating water model. The diffusion coefficients of the free ions in an open chain are significantly larger than in periodically replicated wires that necessarily contain D or L end defects, and both are higher than they are in bulk water. The free hydroxide ion diffuses faster than the free hydronium ion in short CNTs, unlike diffusion in liquid water, and both coefficients increase and converge to nearly the same value with increasing tube length. The diffusion coefficients of the two ions increase further when the tubes are immersed in a water reservoir and they move easily out of the tube, suggesting an additional pathway for proton transport via OH- ions in biological channels. (C) 2013 AIP Publishing LLC.