|School or College
|College of Science
|Maity, Dilip K.; Duncan, Wendell T.
|Direct ab initio dynamics studies of the hydrogen abstraction reactions of hydrogen atom with fluoromethanes
|A direct ab initio dynamics study on the gas-phase reactions of atomic hydrogen with different fluoromethanes has been carried out. The thermal rate constants were calculated using canonical variational transition state (CVT) theory augmented by multidimensional semiclassical zero and small curvature tunneling approximations. The potential energy surfaces for the reactions were calculated using hybrid density functional theory, namely, Becke's half-and-half (BH) nonlocal exchange and the Lee?Yang?Parr (LYP) nonlocal correlation functionals using the cc-pVDZ basis set. The reaction energies and barrier heights were improved by single-point energy calculations along the minimum energy path (MEP) at the spin-projected fourth order Moller?Plesset perturbation theory (PMP4) using the cc-pVTZ basis set. The calculated forward and reverse thermal rate constants are in the good agreement with the experimental data. The electronic effects of fluorine substitution on the rate of this class of reactions are examined.
|American Chemical Society
|Hydrogen abstraction reactions; Gas-phase reactions; Fluoromethanes; Thermal rate constants; Moller?Plesset perturbation theory; Hybrid density functional theory
|Molecular dynamics; Density functionals
|Maity, D. K., Duncan, W. T., & Truong, T. (1999). Direct ab initio dynamics studies of the hydrogen abstraction reactions of hydrogen atom with fluoromethanes. Journal of Physical Chemistry A, 103(13), 2152-9.
|(c)American Chemical Society http://dx.doi.org/10.1021/jp984281x