An Ab Initio Based Full-Dimensional Global Potential Energy Surface for FH₂O(X²A′) and Dynamics for the F + H₂O → HF + HO Reaction

Abstract

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..

Department(s)

Chemistry

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)

0021-9606

Document Type

Article - Journal

Document Version

Citation

File Type

text

Language(s)

English

Rights

© 2012 American Institute of Physics (AIP), All rights reserved.

Publication Date

01 Sep 2012

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