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Anchoring the potential energy surface for the Br + H2O → HBr + OH reaction

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Abstract

The forward and reverse reactions Br + H2O → HBr + OH are important in atmospheric and environmental chemistry. Five stationary points on the potential energy surface for the Br + H2O → HBr + OH reaction, including the entrance complex, transition state, and exit complex, have been studied using the CCSD(T) method with correlation-consistent basis sets up to cc-pV5Z-PP. Contrary to the valence isoelectronic F + H2O system, the Br + H2O reaction is endothermic (by 31.8 kcal/mol after zero-point vibrational, relativistic, and spin–orbit corrections), consistent with the experimental reaction enthalpy. The CCSD(T)/cc-pV5Z-PP method predicts that the reverse reaction HBr + HO → Br + H2O has a complex but no classical barrier. When zero-point vibrational energies are added, the transition state lies 0.25 kcal/mol above the separated products. This is consistent with the negative temperature dependence for the rate constant observed in experiments. The entrance complex is predicted to lie 2.6 kcal/mol below separated Br + H2O. The exit complex is predicted to lie 1.8 kcal/mol below separated HBr + OH.

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Acknowledgments

We thank Dr. Gabor Czakó for very helpful discussions. Correspondence with Professors Antonio de Oliveira-Filho and Joel Bowman are sincerely appreciated. This research was supported by Tianjin Natural Science Foundation (11JCYBJC14500), the National Natural Science Foundation of China (Grant No. 10904111), and China Postdoctoral Science Foundation (20100470792), as well as by the U.S. Department of Energy, Office of Basic Energy Sciences, Chemical Sciences Division, Fundamental Interactions Branch.

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Authors and Affiliations

  1. School of Biomedical Engineering, Tianjin Medical University, Tianjin, 300070, People’s Republic of China

    Meiling Zhang

  2. College of Physical Science and Technology, Sichuan University, Chengdu, 610064, Sichuan, People’s Republic of China

    Yanjun Hao

  3. School of Engineering and Technology, Neijiang Normal University, Neijiang, 641112, Sichuan, People’s Republic of China

    Yundong Guo

  4. Center for Computational Quantum Chemistry, University of Georgia, Athens, GA, 30602, USA

    Yaoming Xie & Henry F. Schaefer

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  1. Meiling Zhang
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  2. Yanjun Hao
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  3. Yundong Guo
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  4. Yaoming Xie
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  5. Henry F. Schaefer
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Corresponding author

Correspondence to Henry F. Schaefer.

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Dedicated to the memory of Professor Isaiah Shavitt and published as part of the special collection of articles celebrating his many contributions.

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Zhang, M., Hao, Y., Guo, Y. et al. Anchoring the potential energy surface for the Br + H2O → HBr + OH reaction. Theor Chem Acc 133, 1513 (2014). https://doi.org/10.1007/s00214-014-1513-6

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