title: S-shooting: a Bennett-Chandler-like method for the computation of rate constants from committor trajectories.
abstract: Mechanisms of rare transitions between long-lived stable states are often analyzed in terms of commitment probabilities, determined from swarms of short molecular dynamics trajectories. Here, we present a computer simulation method to determine rate constants from such short trajectories combined with free energy calculations. The method, akin to the Bennett-Chandler approach for the calculation of reaction rate constants, requires the definition of a valid reaction coordinate and can be applied to both under- and overdamped dynamics. We verify the correctness of the algorithm using a one-dimensional random walker in a double-well potential and demonstrate its applicability to complex transitions in condensed systems by calculating cavitation rates for water at negative pressures.
authors.affiliation: Faculty of Physics and Center for Computational Materials Science, University of Vienna, Boltzmanngasse 5, 1090 Vienna, Austria. christoph.dellago@univie.ac.at.
authors.forename: Georg
authors.initials: G
authors.lastname: Menzl
authors.affiliation: Faculty of Physics and Center for Computational Materials Science, University of Vienna, Boltzmanngasse 5, 1090 Vienna, Austria. christoph.dellago@univie.ac.at.
authors.forename: Andreas
authors.initials: A
authors.lastname: Singraber
authors.affiliation: Faculty of Physics and Center for Computational Materials Science, University of Vienna, Boltzmanngasse 5, 1090 Vienna, Austria. christoph.dellago@univie.ac.at.
authors.forename: Christoph
authors.initials: C
authors.lastname: Dellago