Stabilization of a transition state by excited vibration and impact on the reaction rate in the three-body Lennard-Jones system

TL;DR

This paper demonstrates that excited vibrations can dynamically stabilize a transition state in a three-body Lennard-Jones system, affecting reaction rates, with theoretical explanations and molecular dynamics verification.

Contribution

It introduces a novel mechanism of dynamic stabilization of transition states via excited vibrations, supported by theoretical analysis and simulations.

Findings

Transition state can be stabilized by vibrational excitation.

Dynamical stabilization influences reaction rates.

Theoretical and simulation results agree on stabilization effects.

Abstract

The three-body Lennard-Jones system on the plane has a transition state, which is the straight conformation located at a saddle point of the potential energy landscape. We show that the transition state can be dynamically stabilized by excited vibration of particle distances. The stabilization mechanism is explained theoretically, and is verified by performing molecular dynamics simulations. We also examine whether the dynamical stabilization gives an impact on the reaction rate between the two isomers of equilateral triangle conformations by comparing with the transition state theory.