Abstract.
We introduce a path-sampling scheme that allows equilibrium state-ensemble averages to be computed by means of a biased distribution of non-equilibrium paths. This non-equilibrium method is applied to the case of the 38-atom Lennard-Jones atomic cluster, which has a double-funnel energy landscape. We calculate the free energy profile along the Q4 bond orientational order parameter. At high or moderate temperature the results obtained using the non-equilibrium approach are consistent with those obtained using conventional equilibrium methods, including parallel tempering and Wang-Landau Monte Carlo simulations. At lower temperatures, the non-equilibrium approach becomes more efficient in exploring the relevant inherent structures. In particular, the free energy agrees with the predictions of the harmonic superposition approximation.
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Adjanor, G., Athènes, M. & Calvo, F. Free energy landscape from path-sampling: application to the structural transition in LJ38 . Eur. Phys. J. B 53, 47–60 (2006). https://doi.org/10.1140/epjb/e2006-00353-0
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DOI: https://doi.org/10.1140/epjb/e2006-00353-0