Atomistic analysis of nematic phase transition in 4-cyano-4'-n-alkyl biphenyl liquid crystals: Sampling for the first-order phase transition and the free-energy decomposition.

Molecular dynamics simulations were conducted using the generalized replica exchange method (gREM) on the 4-cyano-4'-n-alkyl biphenyl (nCB) system with n = 5, 6, 7, and 8, which exhibits a nematic-isotropic (NI) phase transition. Sampling near the phase transition temperature in systems undergoing first-order phase transitions, such as the NI phase transition, is demanding due to the substantial energy gap between the two phases. To address this, gREM, specifically designed for first-order phase transitions, was utilized to enhance sampling near the NI phase transition temperature.