Crystal nucleation of hard spheres using molecular dynamics, umbrella sampling and forward flux sampling: A comparison of simulation techniques

Abstract: Over the last number of years several simulation methods have been introduced to study rare events such as nucleation. In this paper we examine the crystal nucleation rate of hard spheres using three such numerical techniques: molecular dynamics, forward flux sampling and a Bennett-Chandler type theory where the nucleation barrier is determined using umbrella sampling simulations. The resulting nucleation rates are compared with the experimental rates of Harland and Van Megen [J. L. Harland and W. van Megen, Phys. Rev. E 55, 3054 (1997)], Sinn et al. [C. Sinn et al., Prog. Colloid Polym. Sci. 118, 266 (2001)] and Schatzel and Ackerson [K. Schatzel and B.J. Ackerson, Phys. Rev. E, 48, 3766 (1993)] and the predicted rates for monodisperse and 5% polydisperse hard spheres of Auer and Frenkel [S. Auer and D. Frenkel, Nature 409, 1020 (2001)]. When the rates are examined in long-time diffusion units, we find agreement between all the theoretically predicted nucleation rates, however, the experimental results display a markedly different behaviour for low supersaturation. Additionally, we examined the pre-critical nuclei arising in the molecular dynamics, forward flux sampling, and umbrella sampling simulations. The structure of the nuclei appear independent of the simulation method, and in all cases, the nuclei contain on average significantly more face-centered-cubic ordered particles than hexagonal-close-packed ordered particles.