Issue 31, 2012
From the journal:

Physical Chemistry Chemical Physics

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

Guoliang Li,a   Liqing Zhou,a   Qian-Shu Li,*a   Yaoming Xieb  and  Henry F. Schaefer, III*b  

* Corresponding authors

a MOE Key Laboratory of Theoretical Chemistry of the Environment, Center for Computational Quantum Chemistry, South China Normal University, Guangzhou 510006, P. R. China
E-mail: qsli@scnu.edu.cn

b Center for Computational Quantum Chemistry, University of Georgia, Athens, USA
E-mail: fri@uga.edu

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

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Article information

DOI
https://doi.org/10.1039/C2CP41555K
Article type
Communication
Submitted
29 Mar 2012
Accepted
12 Jun 2012
First published
18 Jun 2012

Phys. Chem. Chem. Phys., 2012,14, 10891-10895

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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

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