Anomalous Dynamics of Water in Polyamide Matrix

摘要

Water in polymer matrixes is likely to show anomalous dynamics, a problem that has not been well understood yet. Here, we performed atomistic molecular dynamics simulations to study the water dynamics in a polyamide (PA) matrix, the bulk phase of well-known reverse osmosis membranes. For time-dependent ensemble average, water molecules experienced ballistic diffusion at a shorter time scale, followed by a crossover from subdiffusion to Brownian diffusion at a time scale similar to 10 ns, and non-Gaussian diffusion, an indication of anomalous dynamics, sticks on even in the Brownian diffusion region. The anomalous dynamics mainly originates from two distinct motions including small-step continuous diffusion and jumping diffusion. The jumping motion has a mean length of 3.08 +/- 0.31 angstrom and characteristic relaxation time of 0.218 +/- 0.040 ns, which dominates the water diffusion in a fully hydrated PA matrix. It comprised low- and high-frequency jumps; the former is almost unchanged, and the latter remarkably increases with the increase of the hydration level. Surrounding neighbors of water strongly affect the jumping frequency, which exponentially or linearly decays with the increase in the number of atoms from the PA matrix. Although the PA matrix is flexible, associated with the water dynamics, the translocation of water is mainly through either tracing the position of neighboring water or jumping into the adjacent accommodation space.