An Ab Initio Based Full-Dimensional Global Potential Energy Surface for FH₂O(X²A′) and Dynamics for the F + H₂O → HF + HO Reaction
A global potential energy surface (PES) for the ground electronic state of FH 2O is constructed based on more than 30 000 ab initio points at the multi-reference configuration interaction level. The PES features a pre-reaction van der Waals well and two post-reaction hydrogen-bonded complexes, as well as a reactant-like transition state with a classical barrier of 3.8 kcalmol. The adiabatic F H 2O →HF OH reaction dynamics on this PES was investigated using a standard quasi-classical trajectory method. In agreement with experiment, the HF product contains significant vibrational excitation with limited rotational excitation, while the OH product is internally cold, reflecting its spectator role in the reaction. The products are primarily scattered in the backward direction, consistent with a direct abstraction mechanism..
J. Li et al., "An Ab Initio Based Full-Dimensional Global Potential Energy Surface for FH₂O(X²A′) and Dynamics for the F + H₂O → HF + HO Reaction," Journal of Chemical Physics, vol. 137, no. 9, American Institute of Physics (AIP), Sep 2012.
The definitive version is available at http://dx.doi.org/10.1063/1.4748857
Keywords and Phrases
Ab initio; Abstraction mechanism; Global potential energy surfaces; Ground electronic state; Hydrogen-bonded complexes; Multireference configuration; OH reaction; Post reaction; Pre-reactions; Quasi-classical trajectory method; Rotational excitation; Transition state; Van der waals; Vibrational excitation, Dynamics; Hydrogen bonds; Quantum chemistry; Van der Waals forces, Potential energy surfaces
International Standard Serial Number (ISSN)
Article - Journal
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