Sulfur dioxide and hypohalous acids (HOX, X=F, Cl, Br, I) are ubiquitous molecules in the atmosphere that are central to important processes like seasonal ozone depletion, acid rain, and cloud nucleation. We present the first theoretical examination of the HOX⋯SO2binary complexes and the associated trends due to halogen substitution. Reliable geometries were optimized at the CCSD(T)/aug‐cc‐pV(T+d)Z level of theory for HOF and HOCl complexes. The HOBr and HOI complexes were optimized at the CCSD(T)/aug‐cc‐pV(D+d)Z level of theory with the exception of the Br and I atoms which were modeled with an aug‐cc‐pwCVDZ‐PP pseudopotential. 27 HOX⋯SO2complexes were characterized and the focal point method was employed to produce CCSDT(Q)/CBS interaction energies. Natural Bond Orbital analysis and Symmetry Adapted Perturbation Theory were used to classify the nature of each principle interaction. The interaction energies of all HOX⋯SO2complexes in this study ranged from 1.35 to 3.81 kcal mol−1. The single‐interaction hydrogen bonded complexes spanned a range of 2.62 to 3.07 kcal mol−1, while the single‐interaction halogen bonded complexes were far more sensitive to halogen substitution ranging from 1.35 to 3.06 kcal mol−1, indicating that the two types of interactions are extremely competitive for heavier halogens. Our results provide insight into the interactions between HOX and SO2which may guide further research of related systems.
The Grimme‐D3 semi‐empirical dispersion energy correction has been implemented for the original effective fragment potential for water (EFP1), and for systems that contain water molecules described by both correlated
- NSF-PAR ID:
- 10078320
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Journal of Computational Chemistry
- Volume:
- 40
- Issue:
- 2
- ISSN:
- 0192-8651
- Format(s):
- Medium: X Size: p. 310-315
- Size(s):
- p. 310-315
- Sponsoring Org:
- National Science Foundation
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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.more » « less
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