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J Chem Phys. 2020 Feb 28;152(8):084104. doi: 10.1063/1.5139228.

Microcanonical coarse-graining of the kinetic Ising model.

Author information

1
dPET, Spokane, Washington 99223, USA.
2
Department of Chemistry, Temple University, Philadelphia, Pennsylvania 19122, USA.
3
Institute for Computational Molecular Science, College of Science and Technology, Temple University, Philadelphia, Pennsylvania 19122, USA.

Abstract

We propose a scheme for coarse-graining the dynamics of the 2-D kinetic Ising model onto the microcanonical ensemble. At subcritical temperatures, 2-D and higher-dimensional Ising lattices possess two basins of attraction separated by a free energy barrier. Projecting onto the microcanonical ensemble has the advantage that the dependence of the crossing rate constant on environmental conditions can be obtained from a single Monte Carlo trajectory. Using various numerical methods, we computed the forward rate constants of coarse-grained representations of the Ising model and compared them with the true value obtained from brute force simulation. While coarse-graining preserves detailed balance, the computed rate constants for barrier heights between 5 kT and 9 kT were consistently 50% larger than the true value. Markovianity testing revealed loss of dynamical memory, which we propose accounts for coarse-graining error. Committor analysis did not support the alternative hypothesis that microcanonical projection is incompatible with an optimal reaction coordinate. The correct crossing rate constant was obtained by spectrally decomposing the diffusion coefficient near the free energy barrier and selecting the slowest (reactive) component. The spectral method also yielded the correct rate constant in the 3-D Ising lattice, where coarse-graining error was 6% and memory effects were diminished. We conclude that microcanonical coarse-graining supplemented by spectral analysis of short-term barrier fluctuations provides a comprehensive kinetic description of barrier crossing in a non-inertial continuous-time jump process.

PMID:
32113343
PMCID:
PMC7042020
[Available on 2021-02-28]
DOI:
10.1063/1.5139228

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