Jump to main content
Jump to site search

Issue 11, 2019
Previous Article Next Article

A comparison between hydrogen and halogen bonding: the hypohalous acid–water dimers, HOX⋯H2O (X = F, Cl, Br)

Author affiliations

Abstract

Hypohalous acids (HOX) are a class of molecules that play a key role in the atmospheric seasonal depletion of ozone and have the ability to form both hydrogen and halogen bonds. The interactions between the HOX monomers (X = F, Cl, Br) and water have been studied at the CCSD(T)/aug-cc-pVTZ level of theory with the spin free X2C-1e method to account for scalar relativistic effects. Focal point analysis was used to determine CCSDT(Q)/CBS dissociation energies. The anti hydrogen bonded dimers were found with interaction energies of −5.62 kcal mol−1, −5.56 kcal mol−1, and −4.97 kcal mol−1 for X = F, Cl, and Br, respectively. The weaker halogen bonded dimers were found to have interaction energies of −1.71 kcal mol−1 and −3.03 kcal mol−1 for X = Cl and Br, respectively. Natural bond orbital analysis and symmetry adapted perturbation theory were used to discern the nature of the halogen and hydrogen bonds and trends due to halogen substitution. The halogen bonds were determined to be weaker than the analogous hydrogen bonds in all cases but close enough in energy to be relevant, significantly more so with increasing halogen size.

Graphical abstract: A comparison between hydrogen and halogen bonding: the hypohalous acid–water dimers, HOX⋯H2O (X = F, Cl, Br)

Back to tab navigation

Supplementary files

Publication details

The article was received on 22 Jan 2019, accepted on 19 Feb 2019 and first published on 20 Feb 2019


Article type: Paper
DOI: 10.1039/C9CP00422J
Citation: Phys. Chem. Chem. Phys., 2019,21, 6160-6170

  •   Request permissions

    A comparison between hydrogen and halogen bonding: the hypohalous acid–water dimers, HOX⋯H2O (X = F, Cl, Br)

    M. E. Wolf, B. Zhang, J. M. Turney and H. F. Schaefer, Phys. Chem. Chem. Phys., 2019, 21, 6160
    DOI: 10.1039/C9CP00422J

Search articles by author

Spotlight

Advertisements