Communication: an existence test for dividing surfaces without recrossing

Ryan Gotchy Mullen; Joan-Emma Shea; Baron Peters

doi:10.1063/1.4862504

Communication: an existence test for dividing surfaces without recrossing

J Chem Phys. 2014 Jan 28;140(4):041104. doi: 10.1063/1.4862504.

Authors

Ryan Gotchy Mullen¹, Joan-Emma Shea², Baron Peters¹

Affiliations

¹ Department of Chemical Engineering, University of California, Santa Barbara, California 93106, USA.
² Department of Chemistry and Biochemistry, University of California, Santa Barbara, California 93106, USA.

PMID: 25669495
DOI: 10.1063/1.4862504

Abstract

The claim that Grote-Hynes theory (GHT), when it provides accurate rates, is equivalent to multidimensional variational transition state theory (VTST) has been debated for decades with convincing arguments on both sides. For the two theories to be equivalent a perfect dividing surface with no recrossing must exist. We describe an easily implemented test employing deterministic microcanonical (NVE) trajectories which can identify situations where no perfect dividing surface exists and thereby potentially falsify the claim of equivalence. We use this test to reach data-supported conclusions about the relationship between GHT and VTST.