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

  • Meiling Zhang
  • Yanjun Hao
  • Yundong Guo
  • Yaoming Xie
  • Henry F. Schaefer
Regular Article
Part of the following topical collections:
  1. Shavitt Memorial Festschrift Collection

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.

Keywords

Atmospheric chemistry Water reactions Bromine atoms OH radicals Potential energy surfaces Ab initio computations 

Notes

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.

Supplementary material

214_2014_1513_MOESM1_ESM.doc (2.1 mb)
Supplementary material 1 (doc 2148 kb)

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Copyright information

© Springer-Verlag Berlin Heidelberg 2014

Authors and Affiliations

  • Meiling Zhang
    • 1
  • Yanjun Hao
    • 2
  • Yundong Guo
    • 3
  • Yaoming Xie
    • 4
  • Henry F. Schaefer
    • 4
  1. 1.School of Biomedical EngineeringTianjin Medical UniversityTianjinPeople’s Republic of China
  2. 2.College of Physical Science and TechnologySichuan UniversityChengduPeople’s Republic of China
  3. 3.School of Engineering and TechnologyNeijiang Normal UniversityNeijiangPeople’s Republic of China
  4. 4.Center for Computational Quantum ChemistryUniversity of GeorgiaAthensUSA

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