Seeding Method for Ice Nucleation under Shear

Abstract

Hydrodynamic flow can have complex and far-reaching consequences on the rate of homogenous nucleation. We present a general formalism for calculating the nucleation rates of simply sheared systems. We have derived an extension to the conventional Classical Nucleation Theory, explicitly embodying the shear rate. Seeded Molecular Dynamics simulations form the backbone of our approach. The framework can be used for moderate supercoolings, at which temperatures brute-force methods are practically infeasible. The competing energetic and kinetic effects of shear arise naturally from the equations. We show how the theory can be used to identify shear regimes of ice nucleation behaviour for the mW water model, unifying disparate trends reported in the literature. At each temperature, we define a crossover shear rate in the limit of 1000 − 10, 000 s −1 , beyond which the nucleation rate increases steadily upto a maximum, at the optimal shear rate. For 235, 240, 255 and 260 K, the optimal shear rates are in the range of ≈ 10 6 − 10 7 s −1 . For very high shear rates beyond 10 8 s −1 , nucleation is strongly inhibited. Our results indicate that the shear-dependent nucleation rate curves have a non-monotonic dependence on temperature.