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Hemibond complexes between H2S and free radicals (F, Cl, Br, and OH)

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Abstract

The interaction of hydrogen sulfide (H2S) with F, Cl, Br, and OH is investigated using ab initio methods to identify the two-center three-electron hemibond responsible for their complexation. The binding energies are found to be stronger than those in the analogous water complexes, but follow the same trend of increasing strength: F > Cl > Br > OH. The radicals are located nearly perpendicular to the H2S plane forming an angle of about 90°. Analysis of molecular orbitals and natural bond orbitals are carried out to understand the energetics, structures, and bonding characteristics of these hemibonded complexes.

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Acknowledgments

This work was supported by the Department of Energy (DE-FG02-05ER15694). The computations were performed at the National Energy Research Scientific Computing (NERSC) Center.

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Authors and Affiliations

  1. Department of Chemistry and Chemical Biology, University of New Mexico, Albuquerque, NM, 87131, USA

    Benjamin Alday, Ryan Johnson, Jun Li & Hua Guo

Authors
  1. Benjamin Alday
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  2. Ryan Johnson
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  3. Jun Li
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  4. Hua Guo
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Corresponding author

Correspondence to Hua Guo.

Additional information

Dedicated to Professor Guosen Yan and published as part of the special collection of articles celebrating his 85th birthday.

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Alday, B., Johnson, R., Li, J. et al. Hemibond complexes between H2S and free radicals (F, Cl, Br, and OH). Theor Chem Acc 133, 1540 (2014). https://doi.org/10.1007/s00214-014-1540-3

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  • DOI: https://doi.org/10.1007/s00214-014-1540-3

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