Caveats of mean first-passage time methods applied to the crystallization transition: Effects of non-Markovianity

Swetlana Jungblut; Christoph Dellago

doi:10.1063/1.4907364

Caveats of mean first-passage time methods applied to the crystallization transition: Effects of non-Markovianity

J Chem Phys. 2015 Feb 14;142(6):064103. doi: 10.1063/1.4907364.

Authors

Swetlana Jungblut¹, Christoph Dellago¹

Affiliation

¹ Faculty of Physics, University of Vienna, Boltzmanngasse 5, 1090 Wien, Austria.

PMID: 25681883
DOI: 10.1063/1.4907364

Abstract

Using the crystallization transition in a Lennard-Jones fluid as example, we show that mean first-passage time based methods may underestimate the reaction rates. We trace the reason of this deficiency back to the non-Markovian character of the dynamics caused by the projection to a poorly chosen reaction coordinate. The non-Markovianity of the dynamics becomes apparent in the behavior of the recurrence times.