Skip to main content
Article
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
  • Jun Li
  • Richard Dawes, Missouri University of Science and Technology
  • Hua Guo
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
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
9-1-2012
Disciplines
Citation Information
Jun Li, Richard Dawes and Hua Guo. "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 Iss. 9 (2012) ISSN: 0021-9606
Available at: http://works.bepress.com/richard_dawes/40/