Theoretical kinetic analysis and molecular dynamic simulations for exploring the dissociation pathways of CF3OH

Abstract

The unimolecular dissociation of trifluoromethanol (CF3OH) had been studied by static and dynamic calculations. The electronic structure calculations and molecular dynamic (MD) simulations were performed at the second order Moller-Plesset perturbation theory (MP2) theory. The kinetic behavior was investigated in the temperature range from 298 to 1400 K and pressure range between 10−9 to 104 kPa using Troe’s formalism. In addition to this, Born-Oppenheimer molecular dynamic (BOMD) model was employed for exploring the dynamic insights of the reaction. Reaction trajectories were estimated by microcanonical normal mode sampling, wherein selected vibrational modes were pumped with additional energy of 95, 155, and 208 kcal mol−1. Our calculations suggest that, the unimolecular decomposition of CF3OH results in the generation of molecular HF with concomitant generation of CF2O via intramolecular reaction. The MD simulations suggest the critical role of vibrational modes for such intramolecular reaction.