Extension of the lattice-based aggregation-volume-bias Monte Carlo approach to molecular crystals: Quantitative calculations on the thermodynamic stability of the urea polymorphs

Abstract

Motivated by the recent success in using a latticed-based version of the aggregation-volume-bias Monte Carlo method to determine the thermodynamic stabilities of both bcc and fcc clusters formed by Lennard-Jones particles, this approach is extended to the calculation of the nucleation-free energies of solid clusters formed by urea at 300 K in two different polymorphs, i.e., form I and form IV. In addition to the lattice confinement, the constraint on the molecular orientation was found necessary to ensure that the clusters sampled in these simulations are in the corresponding form. A model that can reproduce the experimental properties such as density and lattice parameters of form I at ambient conditions is used in this study. From the size dependencies of the free energies obtained for a finite set of clusters studied, the free energies of clusters at other sizes, including an infinitely large cluster, were extrapolated. At the infinite size, equivalent to a bulk solid, form I was found to be more stable than form IV, which agrees with the experimental results. In addition, form I was found to be thermodynamically stable throughout the entire cluster size range investigated here, which contradicts the previous finding that small form I clusters are unstable from the crystal nucleation simulation studies.