Relaxation Augmented Free Energy Perturbation
Chemical Physics
2019-10-01 v3
Abstract
Inspired by the recent development on calculating the free energy change via a relaxation process [Nat. Phys. 14, 842 (2018)], we investigate the role of heat released in an irreversible relaxation following a large perturbation. Utilizing a derivation without microscopic reversibility, we arrive at a new free energy estimator that employs a volume term to account for missing important rare events. Applications to harmonic oscillators and particle insertion in Lennard-Jones fluid agree well with the (numerical) exact solutions. Our study hence suggests an alternative interpretation to the insufficient sampling problem in free energy calculations.
Cite
@article{arxiv.1811.09707,
title = {Relaxation Augmented Free Energy Perturbation},
author = {Ying-Chih Chiang and Livia B. Pártay and Guanglian Li and Christopher Cave-Ayland and Marley L. Samways and Frank Otto and Jonathan W. Essex},
journal= {arXiv preprint arXiv:1811.09707},
year = {2019}
}