Boxed molecular dynamics as a tool for unimolecular rate theory R J Shannon, M A Blitz and P W Seakins School of Chemistry, University of Leeds, UK Typically, the commonly encountered rare event problem prevents molecular dynamics from being a useful tool for investigating gas phase unimolecular kinetics. Utilising the recently developed path-based, multi-dimensional, boxed molecular dynamics method (BXD-path), we explore the feasibility of accelerated molecular dynamics for obtaining unimolecular rate coefficients for a small gas phase system. This poster will present a "like for like" comparison between statistical and dynamical studies of a problematic RO2 to QOOH isomerisation via a ring structure saddle point. We will compare BXD-path rate coefficients with RRKM results utilising a variety of models for defining the rovibrational density of states (DOS). We will also explore whether BXD based methodologies could be used to obtain efficient fully-coupled, anharmonic corrections to harmonic densities of states typically used in RRKM calculations.
P21
© The Author(s), 2022
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