Simultaneous estimation of free energies and rates using forward flux sampling and mean first passage times

In this work, a method is proposed to simultaneously compute the transition rate constant and the free energy profile of a rare event along an order parameter connecting two well-defined regions of phase space. The method employs a forward flux sampling technique in combination with a mean first pas...

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Bibliographic Details
Published in:The Journal of chemical physics 2015-12, Vol.143 (24), p.244113-244113
Main Authors: Thapar, Vikram, Escobedo, Fernando A
Format: Article
Language:English
Subjects:
Free energy
Ising model
Markov analysis
Markov chains
Nucleation
Order parameters
Physics
Potential energy
Sampling
Solid phases
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Summary:In this work, a method is proposed to simultaneously compute the transition rate constant and the free energy profile of a rare event along an order parameter connecting two well-defined regions of phase space. The method employs a forward flux sampling technique in combination with a mean first passage time approach to estimate the steady state probability and mean first passage times. These quantities are fitted to a Markovian model that allows the estimation of the free energy along the chosen order parameter. The proposed technique is first validated with two test systems (an Ising model and a model potential energy surface) and then used to study the solid-phase homogeneous nucleation of selected polyhedral particles.
ISSN:0021-9606
1089-7690
DOI:10.1063/1.4938248