Classical trajectory simulations of post-transition state dynamics

Upakarasamy Lourderaj, Kyoyeon Park, William L. Hase

Research output: Contribution to journalReview articlepeer-review

110 Scopus citations

Abstract

Classical chemical dynamics simulations of post-transition state dynamics are reviewed. Most of the simulations involve direct dynamics for which the potential energy and gradient are obtained directly from an electronic structure theory. The chemical reaction attributes and chemical systems presented are product energy partitioning for Cl- ⋯ CH3Br → ClCH3 + Br- and C2H5F → C2H4 + HF dissociation, non-RRKM dynamics for cyclopropane stereomutation and the Cl- ⋯ CH3Cl complexes mediating the Cl- + CH3Cl SN2 nucleophilic substitution reaction, and non-IRC dynamics for the OH- + CH3F and F- + CH3OOH chemical reactions. These studies illustrate the important role of chemical dynamics simulations in understanding atomic-level reaction dynamics and interpreting experiments. They also show that widely used paradigms and model theories for interpreting reaction kinetics and dynamics are often inaccurate and are not applicable.

Original languageEnglish
Pages (from-to)361-403
Number of pages43
JournalInternational Reviews in Physical Chemistry
Volume27
Issue number3
DOIs
StatePublished - Jul 2008

Keywords

  • Chemical dynamics
  • Non-IRC dynamics
  • Non-RRKM dynamics
  • Potential energy surfaces
  • Unimolecular reaction dynamics

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