Title

A Reactive Molecular Dynamics Study of the Thermal Decomposition of Perfluorodimethyl Ether

Document Type

Article

Publication Date

4-2009

Abstract

Classical reactive molecular dynamics (RMD) simulation is used to model the thermal decomposition of perfluorodimethyl ether (CF3OCF3), which is relevant as a simple molecule containing the necessary architectural elements to study the chemical stability of perfluoropolyether lubricants. The RMD algorithm employs nonreactive interaction potentials for the reactants and products. The reactivity is implemented through a coarse-grained simulation algorithm, incorporating elements from both the quantum and macroscopic descriptions of the reaction. The RMD scheme maps the quantum mechanically determined transition state onto a set of geometric triggers. When a configuration matching those triggers is found in the RMD simulation, the reaction instantaneously occurs. A brief, local equilibration process stabilizes the configuration, and the simulation continues. Using two geometric triggers, the RMD simulation can describe quantitatively the temperature dependence of the thermal decomposition of CF3OCF3, when compared to the quantum mechanical standard.

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