Dynamics and decay rates of a time-dependent two-saddle system

Johannes Reiff; Matthias Feldmaier; Jörg Main; Rigoberto Hernandez

doi:10.1103/PhysRevE.103.022121

Dynamics and decay rates of a time-dependent two-saddle system

Phys Rev E. 2021 Feb;103(2-1):022121. doi: 10.1103/PhysRevE.103.022121.

Authors

Johannes Reiff¹, Matthias Feldmaier¹, Jörg Main¹, Rigoberto Hernandez^{2

3}

Affiliations

¹ Institut für Theoretische Physik I, Universität Stuttgart, 70550 Stuttgart, Germany.
² Department of Chemistry, Johns Hopkins University, Baltimore, Maryland 21218, USA.
³ Departments of Chemical & Biomolecular Engineering, and Materials Science and Engineering, Johns Hopkins University, Baltimore, Maryland 21218, USA.

PMID: 33736042
DOI: 10.1103/PhysRevE.103.022121

Abstract

The framework of transition state theory (TST) provides a powerful way for analyzing the dynamics of physical and chemical reactions. While TST has already been successfully used to obtain reaction rates for systems with a single time-dependent saddle point, multiple driven saddles have proven challenging because of their fractal-like phase space structure. This paper presents the construction of an approximately recrossing-free dividing surface based on the normally hyperbolic invariant manifold in a time-dependent two-saddle model system. Based on this, multiple methods for obtaining instantaneous (time-resolved) decay rates of the underlying activated complex are presented and their results discussed.