Hysteresis Elimination for an Anisotropic Liquid-Crystal Model via Molecule Design and Replica-Exchange Optimization

The phenomenon of hysteresis in simulations, in which a system’s current state is correlated to previous states and inhibits the transition to a more stable phase, may often lead to misleading results in physical chemistry. In this study, in addition to the replica exchange method (REM), a novel approach was taken by combining an evolution strategy based on the evolutionary principles of nature to predict phase transitions for the Hess–Su liquid-crystal model. In this model, an anisotropy term is added to the simple 6-12 Lennard-Jones model to intuitively reproduce the behavior of liquid crystals. We first applied the pressure–temperature REM to the Hess–Su model and optimized the replica spacing for the energy distribution to gain the maximum advantage from the REM. We then used the same approach as for the Hamiltonian REM, seeking to optimize the replica spacing in the same way. Based on both results, we attempted to predict this coarse-grained liquid-crystal model’s exact phase transition point. In the Hamiltonian REM, replicas were prepared with different molecular aspect ratios corresponding to the values of the anisotropy terms in the potential function. The Hess–Su liquid-crystal model, which undergoes a direct transition from the nematic to the solid phase without going through a smectic phase, is a challenging research target for understanding phase transitions. Despite the tremendous computational difficulty in overcoming the strong hysteresis present in this system, our method could predict the phase transition point clearly and significantly reduce the extent of hysteresis. Our approach is beneficial when simulating more complex systems and, above all, shows great potential for more accurate and efficient phase transition predictions in the field of molecular simulation in the future.