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Abstract
摘要 |
The Jarzynski equality (JE), which relates the work of a non-equilibrium process to the free energy difference between its initial and final states, provides an efficient way to calculate free energies of thermodynamic systems in simulations or experiments. However, more extensive applications of the JE are hindered by the requirement that the initial state must be in equilibrium. We extend the JE to be the Jarzynski matrix equality (JME) which relates the work of trajectories connecting metastable conformational regions to their local free energies, and thus we can estimate the free energy from the non-equilibrium trajectories starting from an almost arbitrary initial distribution. We also combine the JME with the re-weighted ensemble dynamics method to form a general non-equilibrium enhanced sampling technique, named as the re-weighted nonequilibrium ensemble dynamics (RNED) to efficiently sample complicate conformational space. We have illustrated the validity and efficiency of the JME and RNED in toy models, Lennard-Jones fluids, and polymer chain models. |
