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Title: Sulfurous and sulfonic acids: Predicting the infrared spectrum and setting the surface straight

Journal Article · · Journal of Chemical Physics
DOI: https://doi.org/10.1063/1.5133954 · OSTI ID:1779052
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]
  1. Univ. of Georgia, Athens, GA (United States)
  2. Argonne National Lab. (ANL), Argonne, IL (United States)
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Sulfurous acid (H2SO3) is an infamously elusive molecule. Although some theoretical papers have supposed possible roles for it in more complicated systems, it has yet to be experimentally observed. To aid experiment in detecting this molecule, we have examined the H2O + SO2 potential energy surface at the CCSDT(Q)/CBS//CCSD(T)-F12b/cc-pVTZ-F12b level of theory to resolve standing discrepancies in previous reports and predict the gas-phase vibrational spectrum for H2SO3. We find that sulfurous acid has two potentially detectable rotamers, separated by 1.1 kcal mol-1 ΔH-0K with a torsional barrier of 1.6 kcal mol-1. The sulfonic acid isomer is only 6.9 kcal mol-1 above the lowest enthalpy sulfurous acid rotamer, but the barrier to form it is 57.2 kcal mol-1. Error in previous reports can be attributed to misidentified stationary points, the use of density functionals that perform poorly for this system, and, most importantly, the basis set sensitivity of sulfur. Using VPT2+K, we determine that the intense S=O stretch fundamental of each species is separated from other intense peaks by at least 25 cm-1, providing a target for identification by infrared spectroscopy. Published under license by AIP Publishing.

Research Organization:
Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Organization:
USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division
Grant/Contract Number:
AC02-06CH11357; SC0018412
OSTI ID:
1779052
Journal Information:
Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 2 Vol. 152; ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)Copyright Statement
Country of Publication:
United States
Language:
English

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