Jump to main content
Jump to site search

Issue 31, 2012
Previous Article Next Article

The entrance complex, transition state, and exit complex for the F + H2O → HF + OH reaction. Definitive predictions. Comparison with popular density functional methods

Author affiliations

Abstract

Following the H + H2 and F + H2 reactions, the fluorine atom – water system has the potential to become one of the best understood chemical reactions. Stationary points for the F + H2O potential energy surface have been located with the “Gold Standard” CCSD(T) method using the Dunning correlation consistent basis sets through quintuple zeta. The CCSD(T)/cc-pV5Z barrier height is prediced to be 2.5 kcal mol−1, less than previous estimates of 4–7 kcal mol−1. From higher level theoretical studies of the prototypical F + H2 reaction, this barrier should be less than 0.5 kcal mol−1 above the exact, nonrelativistic classical barrier height. 41 of the 49 DFT methods applied to F + H2O predict no barrier at all. The eight DFT methods that do predict a barrier show exothermicities that are somewhat too small. The CCSD(T)/cc-pV5Z entrance complex is bound by 3.4 kcal mol−1 relative to separated F + H2O. The analogous exit complex is bound by 5.9 kcal mol−1 relative to separated HF + OH.

Graphical abstract: The entrance complex, transition state, and exit complex for the F + H2O → HF + OH reaction. Definitive predictions. Comparison with popular density functional methods

Back to tab navigation

Publication details

The article was received on 29 Mar 2012, accepted on 12 Jun 2012 and first published on 18 Jun 2012


Article type: Communication
DOI: 10.1039/C2CP41555K
Citation: Phys. Chem. Chem. Phys., 2012,14, 10891-10895
  •   Request permissions

    The entrance complex, transition state, and exit complex for the F + H2O → HF + OH reaction. Definitive predictions. Comparison with popular density functional methods

    G. Li, L. Zhou, Q. Li, Y. Xie and H. F. Schaefer, Phys. Chem. Chem. Phys., 2012, 14, 10891
    DOI: 10.1039/C2CP41555K

Search articles by author

Spotlight

Advertisements