The mechanism of rare events in complex systems can be found by sampling dynamical paths that connect stable states. To calculate a rate using transition paths, an order parameter is required to describe the progress of the reaction and to distinguish the initial and final states. In this work, we compare two implementations of transition path sampling for Langevin paths, one for which paths are sampled in configuration space and the other in the space of the random variables that describe the thermostat. These two approaches are found to give different rates for the rearrangement of a seven-particle cluster despite the fact that both are formally exact. The difference is understood in terms of how efficiently the methods sample states along the order parameter. The more efficient approach takes the system to unexpected states that are allowed by a poor choice of order parameter. While transition path sampling is formally correct, we show how mistakes can be made when the system escapes to unknown states along an order parameter represented in terms of collective variables.
Skip Nav Destination
,
,
Article navigation
21 August 2009
Research Article|
August 19 2009
Pitfalls of choosing an order parameter for rare event calculations
Bradley M. Dickson;
Bradley M. Dickson
a)
Department of Chemistry and Biochemistry and Institute for Computational Engineering and Sciences,
University of Texas at Austin
, Austin, Texas 78712, USA
Search for other works by this author on:
Dmitrii E. Makarov;
Dmitrii E. Makarov
Department of Chemistry and Biochemistry and Institute for Computational Engineering and Sciences,
University of Texas at Austin
, Austin, Texas 78712, USA
Search for other works by this author on:
Graeme Henkelman
Graeme Henkelman
b)
Department of Chemistry and Biochemistry and Institute for Computational Engineering and Sciences,
University of Texas at Austin
, Austin, Texas 78712, USA
Search for other works by this author on:
Bradley M. Dickson
a)
Dmitrii E. Makarov
Graeme Henkelman
b)
Department of Chemistry and Biochemistry and Institute for Computational Engineering and Sciences,
University of Texas at Austin
, Austin, Texas 78712, USA
a)
Electronic mail: [email protected].
b)
Electronic mail: [email protected].
J. Chem. Phys. 131, 074108 (2009)
Article history
Received:
May 12 2009
Accepted:
July 22 2009
Citation
Bradley M. Dickson, Dmitrii E. Makarov, Graeme Henkelman; Pitfalls of choosing an order parameter for rare event calculations. J. Chem. Phys. 21 August 2009; 131 (7): 074108. https://doi.org/10.1063/1.3204008
Download citation file:
Pay-Per-View Access
$40.00
Sign In
You could not be signed in. Please check your credentials and make sure you have an active account and try again.
Citing articles via
DeePMD-kit v2: A software package for deep potential models
Jinzhe Zeng, Duo Zhang, et al.
CREST—A program for the exploration of low-energy molecular chemical space
Philipp Pracht, Stefan Grimme, et al.
Related Content
Inferring free-energy barriers and kinetic rates from molecular dynamics via underdamped Langevin models
J. Chem. Phys. (October 2023)
Molecular dynamics saddle search adaptive kinetic Monte Carlo
J. Chem. Phys. (June 2014)
Scaling methods for accelerating kinetic Monte Carlo simulations of chemical reaction networks
J. Chem. Phys. (June 2019)
Building Markov state models along pathways to determine free energies and rates of transitions
J. Chem. Phys. (August 2008)
Selective sampling of transition paths
J. Chem. Phys. (October 2007)