A unified approach to computation of solid and liquid free energy to revisit the solid-fluid equilibrium of Lennard-Jones chains

作者：Vorselaars Bart^*

来源：Journal of Chemical Physics, 2015, 142(11): 114115.

DOI：10.1063/1.4914318

Liquid free energies are computed by integration along a path from a reference system of known free energy, using a strong localization potential. A particular choice of localization pathway is introduced, convenient for use in molecular dynamics codes, and which achieves accurate results without the need to include the identity-swap or relocation Monte Carlo moves used in previous studies. Moreover, an adaptive timestep is introduced to attain the reference system. Furthermore, a center-of-mass correction that is different from previous studies and phase-independent is incorporated. The resulting scheme allows computation of both solid and liquid free energies with only minor differences in simulation protocol. This is used to re-visit solid-liquid equilibrium in a system of short semi-flexible Lennard-Jones chain molecules. The computed melting curve is demonstrated to be consistent with direct co-existence simulations and computed hysteresis loops, provided that an entropic term arising from unsampled solid states is included.

• 出版日期2015-3-21