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Title: Efficient dynamical correction of the transition state theory rate estimate for a flat energy barrier
Authors: Mokkonen, Harri
Ala-Nissila, Tapio
Jonsson, Hannes
Issue Date: 2016
Publisher: © the Authors. Published by AIP Publishing
Citation: MOKKONEN, H., AL-NISSILA, T. and JONSSON, H., 2016. Efficient dynamical correction of the transition state theory rate estimate for a flat energy barrier. Journal of Chemical Physics, 145 : 094901.
Abstract: © 2016 Author(s).The recrossing correction to the transition state theory estimate of a thermal rate can be difficult to calculate when the energy barrier is flat. This problem arises, for example, in polymer escape if the polymer is long enough to stretch between the initial and final state energy wells while the polymer beads undergo diffusive motion back and forth over the barrier. We present an efficient method for evaluating the correction factor by constructing a sequence of hyperplanes starting at the transition state and calculating the probability that the system advances from one hyperplane to another towards the product. This is analogous to what is done in forward flux sampling except that there the hyperplane sequence starts at the initial state. The method is applied to the escape of polymers with up to 64 beads from a potential well. For high temperature, the results are compared with direct Langevin dynamics simulations as well as forward flux sampling and excellent agreement between the three rate estimates is found. The use of a sequence of hyperplanes in the evaluation of the recrossing correction speeds up the calculation by an order of magnitude as compared with the traditional approach. As the temperature is lowered, the direct Langevin dynamics simulations as well as the forward flux simulations become computationally too demanding, while the harmonic transition state theory estimate corrected for recrossings can be calculated without significant increase in the computational effort.
Description: This article may be downloaded for personal use only. Any other use requires prior permission of the author and AIP Publishing. The following article appeared in MOKKONEN, H., AL-NISSILA, T. and JONSSON, H., 2016. Efficient dynamical correction of the transition state theory rate estimate for a flat energy barrier. Journal of Chemical Physics, 145 : 094901 and may be found at https://doi.org/10.1063/1.4962167
Sponsor: This work was supported by the Academy of Finland through the FiDiPro program (H.J. and H.M., Grant No. 263294) and the COMP CoE (T. A-N., Grants Nos. 251748 and 284621).
Version: Published
DOI: 10.1063/1.4962167
URI: https://dspace.lboro.ac.uk/2134/28196
Publisher Link: https://doi.org/10.1063/1.4962167
ISSN: 0021-9606
Appears in Collections:Published Articles (Maths)

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