Investigating rare events with nonequilibrium work measurements. II. Transition and reaction rates

J Chem Phys. 2014 Jan 21;140(3):034115. doi: 10.1063/1.4861056.

Abstract

We present a formalism for investigating transition pathways and transition probabilities for rare events in biomolecular systems. The formalism is based on combining Transition Path Theory with the results of nonequilibrium work relations, and shows that the equilibrium and nonequilibrium transition rates are in fact related. Aside from its fundamental importance, this allows for the calculation of relative equilibrium reaction rates with driven nonequilibrium simulations such as Steered Molecular Dynamics. The workings of the formalism are illustrated with a few typical numerical examples.

Publication types

  • Research Support, U.S. Gov't, Non-P.H.S.

MeSH terms

  • Computer Simulation
  • Dipeptides / chemistry*
  • Models, Chemical
  • Molecular Dynamics Simulation
  • Probability
  • Thermodynamics*

Substances

  • Dipeptides
  • alanylalanine