Different approaches for evaluating exponentially weighted nonequilibrium relations.
The Kawasaki identity (KI) and the Jarzynski equality (JE) are important nonequilibrium relations. Both of these relations take the form of an ensemble average of an exponential function and can exhibit convergence problems when the average of the exponent differs greatly from the log of the average of the exponential function. In this work, we re-express these relations so that only selected regions need to be evaluated in an attempt to avoid these convergence issues. In the context of measuring free energies, we compare our method to the JE and the literature standard approach, the maximum likelihood estimator (MLE), and show that in a system with asymmetric work distributions it can perform as well as the MLE. For the KI, we derive an analog to the MLE to compare with our relation and show that these two new relations improve on the KI and are complimentary to each other.
Queensland Micro- and Nanotechnology Centre, School of Biomolecular and Physical Sciences, Griffith University, Brisbane Qld 4111, Australia. james.reid@griffith.edu.au
James C
JC
Reid
Benjamin V
BV
Cunning
Debra J
DJ
Searles
D000465:Algorithms; D003198:Computer Simulation; D016013:Likelihood Functions; D013816:Thermodynamics