Precision shooting: Sampling long transition pathways

Author(s)
Michael Grünwald, Christoph Dellago, Phillip L. Geissler
Abstract

The kinetics of collective rearrangements in solution, such as protein folding and nanocrystal phase transitions, often involve free energy barriers that are both long and rough. Applying methods of transition path sampling to harvest simulated trajectories that exemplify such processes is typically made difficult by a very low acceptance rate for newly generated trajectories. We address this problem by introducing a new generation algorithm based on the linear short time behavior of small disturbances in phase space. Using this "precision shooting" technique, arbitrarily small disturbances can be propagated in time, and any desired acceptance ratio of shooting moves can be obtained. We demonstrate the method for a simple but computationally problematic isomerization process in a dense liquid of soft spheres. We also discuss its applicability to barrier-crossing events involving metastable intermediate states.

Organisation(s)
Computational and Soft Matter Physics
External organisation(s)
University of California, Berkeley
Journal
Journal of Chemical Physics
Volume
129
No. of pages
8
ISSN
0021-9606
DOI
https://doi.org/10.1063/1.2978000
Publication date
2008
Peer reviewed
Yes
Austrian Fields of Science 2012
103036 Theoretical physics, 103009 Solid state physics, 104022 Theoretical chemistry, 103029 Statistical physics
Portal url
https://ucrisportal.univie.ac.at/en/publications/17223fc9-0563-4c4c-8684-63c73bdb9e8c