Direct ab initio molecular dynamics study of F atom reaction with methane

Abstract

The dynamics of the F + CH₄ → HF + CH₃ and F + CD₄ → DF + CD₃ reactions have been investigated using classical trajectory calculations at the MP2/cc-pvdz level of theory. The trajectories were calculated directly from electronic structure computations, and a Hessian based method with updating was used to integrate the trajectories. Using this method, product rovibrational populations and internal energy distributions were obtained for the F + CH₄ and F + CD₄ reactions. The theoretical results were compared with the available experimental data and previous calculations results. The state distributions of the reaction F + CH₄ in these calculations are in reasonable agreement with the experimental results, which indicates that the experimental behavior of the reaction could be well reproduced by the direct classical trajectory calculations at MP2/cc-pvdz level. As such, the product rovibrational populations and internal energy distributions for the reaction F + CD₄ were predicted. The same degree of agreement between theory and experiment as the F + CH₄ reaction is expected.

Acknowledgements

We are very grateful to Y. Yu and W. H. Xue for many helpful discussions and for their keen interest in this work.