We present a dynamic implementation of the Clausius–Clapeyron integration (CCI) method for mapping out phase-coexistence boundaries through a single atomistic simulation run. In contrast to previous implementations, where the reversible path of coexistence conditions is generated from a series of independent equilibrium simulations, dynamic Clausius–Clapeyron integration (d-CCI) explores an entire coexistence boundary in a single nonequilibrium simulation. The method gives accurately the melting curve for a system of particles interacting through the Lennard-Jones potential. Furthermore, we apply d-CCI to compute the melting curve of an ab initio pair potential for argon and verify earlier studies on the effects of many-body interactions and quantum effects in the melting of argon. The d-CCI method shows to be effective in both applications, giving converged coexistence curves spanning a wide range of thermodynamic states from relatively short nonequilibrium simulations.
Single-simulation determination of phase boundaries: A dynamic Clausius–Clapeyron integration method
Maurice de Koning, Alex Antonelli, Sidney Yip; Single-simulation determination of phase boundaries: A dynamic Clausius–Clapeyron integration method. J. Chem. Phys. 22 December 2001; 115 (24): 11025–11035. https://doi.org/10.1063/1.1420486
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