Optimum protocol for fast-switching free-energy calculations

Author(s)
Philipp Geiger, Christoph Dellago
Abstract

Free-energy differences computed from fast-switching simulations or measurements according to the Jarzynski equation are independent of the particular protocol specifying how the control parameter is changed in time. In contrast, the average work carried out on the system as well the accuracy of the resulting free energy strongly depend on the protocol. Recently, Schmiedl and Seifert [Phys. Rev. Lett. 98, 108301 (2007)] found that protocols that minimize the average work for a given duration of the switching process have discrete steps at the beginning and the end. Here we determine numerically the protocols that minimize the statistical error in the free energy estimate and find that such minimum error protocols have similar discrete jumps. Our analysis shows that the reduction in computational effort achieved by the use of steplike protocols can be considerable. Such large savings of computing time, however, typically occur for parameter ranges in which an application of the Jarzynski equation is impractical due to large statistical errors arising from the exponential work average.

Organisation(s)
Computational and Soft Matter Physics
Journal
Physical Review E
Volume
81
No. of pages
14
ISSN
1539-3755
DOI
https://doi.org/10.1103/PhysRevE.81.021127
Publication date
2010
Peer reviewed
Yes
Austrian Fields of Science 2012
103018 Materials physics
Portal url
https://ucrisportal.univie.ac.at/en/publications/2fab71a7-5fc6-4eaa-bad1-dc828b74ce31