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Hydration Increases the Lifetime of Hso5 and Enhances Its Ability to Act as a Nucleation Precursor – a Computational Study : Volume 9, Issue 10 (25/05/2009)

By Kurtén, T.

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Book Id: WPLBN0003993361
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File Size: Pages 13
Reproduction Date: 2015

Title: Hydration Increases the Lifetime of Hso5 and Enhances Its Ability to Act as a Nucleation Precursor – a Computational Study : Volume 9, Issue 10 (25/05/2009)  
Author: Kurtén, T.
Volume: Vol. 9, Issue 10
Language: English
Subject: Science, Atmospheric, Chemistry
Collections: Periodicals: Journal and Magazine Collection (Contemporary), Copernicus GmbH
Publication Date:
Publisher: Copernicus Gmbh, Göttingen, Germany
Member Page: Copernicus Publications


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Stratmann, F., Berndt, T., & Kurtén, T. (2009). Hydration Increases the Lifetime of Hso5 and Enhances Its Ability to Act as a Nucleation Precursor – a Computational Study : Volume 9, Issue 10 (25/05/2009). Retrieved from

Description: Department of Physics, P.O. Box 64, 00014 University of Helsinki, Helsinki, Finland. Recent experimental findings indicate that HSO5 radicals may play a key role in the nucleation of atmospheric SO2 oxidation products. HSO5 radicals are metastable intermediates formed in the SO2 oxidation process, and their stability and lifetime are, at present, highly uncertain. Previous high-level computational studies have predicted rather low stabilities for HSO5 with respect to dissociation into SO3+HO2, and have predicted the net reaction HSO3+OH→SO3+HO2 to be slightly exothermal. However, these studies have not accounted for hydration of HSO5 or its precursor HSO3. In this study, we have estimated the effect of hydration on the stability and lifetime of HSO5 using the advanced quantum chemical methods CCSD(T) and G3B3. We have computed formation energies and free energies for mono- and dihydrates of OH, HSO3, HSO5, SO3 and HO2, and also reanalyzed the individual steps of the HSO3+O2→HSO5→SO3+HO2 reaction at a higher level of theory than previously published. Our results indicate that hydration is likely to significantly prolong the lifetime of the HSO5 intermediate in atmospheric conditions, thus increasing the probability of reactions that form products with more than one sulfur atom. Kinetic modeling indicates that these results may help explain the experimental observations that a mixture of sulfur-containing products formed from SO2 oxidation by OH radicals nucleates much more effectively than sulfuric acid taken from a liquid reservoir.

Hydration increases the lifetime of HSO5 and enhances its ability to act as a nucleation precursor – a computational study

Andersson, M. P. and Uvdal, P.: New Scale Factors for Harmonic Vibrational Frequencies Using the B3LYP Density Functional Method with the Triple-Z Basis Set 6-311+G(d,p), J. Phys. Chem. A, 109, 2937–2941, 2005.; Aaltonen, E. T. and Francisco, J. S.: HOSO2-H2O Radical Complex and Its Possible Effects on the Production of Sulfuric Acid in the Atmosphere, J. Phys. Chem. A, 107, 1216–1221, 2003.; Ahlrichs, R., Bär, M., Häser, M., Horn, H., and Kölmel, C.: Electronic structure calculations on workstation computers: The program system Turbomole, Chem. Phys. Lett., 162, 165–169, 1989.; Alongi, K. S., Dibble, T. S., Shields, G. C., and Kirschner, K. N.: Exploration of the Potential Energy Surfaces, Prediction of Atmospheric Concentrations, and Prediction of Vibrational Spectra for the HO2\ldots(H2O)$_n$ (n=1–2) Hydrogen Bonded Complexes, J. Phys. Chem. A, 110, 3686–3691, 2006.; Atkinson, R., Baulch, D. L., Cox, R. A., Hampson, R. F., Kerr, J. A., Rossi, M. J., and Troe, J. J.: Evaluated Kinetic, Photochemical and Heterogeneous Data for Atmospheric Chemistry: Supplement V. IUPAC Subcommittee on Gas Kinetic Data Evaluation for Atmospheric Chemistry, Phys. Chem. Ref. Data, 26, 521–1011, 1997.; Baboul, A. G., Curtiss, L. A., Redfern, P. C., and Raghavachari, K.: Gaussian-3 theory using density functional geometries and zero-point energies, J. Chem. Phys., 110, 7650–7658, 1999.; Ball, S. M., Hanson, D. R., Eisele, F. L., and McMurry, P. H.: Laboratory studies of particle nucleation: Initial results for H2SO4, H2O, and NH3 vapors, J. Geophys. Res. D, 104, 23709–23718, 1999.; Becke, A. D.: Density-functional thermochemistry. III. The role of exact exchange, J. Chem. Phys., 98, 5648–5652, 1993.; Benson, D. R., Young, L.-H., Kameel, F. R., and Lee, S.-H.: Laboratory-measured nucleation rates of sulfuric acid and water: binary homogeneous nucleation from the SO2 + OH reaction, Geophys. Res. Lett., 35, L11801, doi:10.1029/2008GL033387, 2008.; Benson, S. W.: Thermochemistry and kinetics of sulphur-containing molecules and radicals, Chem. Rev., 78, 23–35, 1978.; Berndt, T., Böge, O., Stratmann, F., Heintzenberg, J., and Kulmala, M.: Rapid formation of sulfuric acid particles at near-atmospheric conditions, Science, 307, 698–700, 2005.; Berndt, T., Böge, O., and Stratmann, F.: Formation of atmospheric H2SO4/H2O particles in the absence of organics: A laboratory study, Geophys. Res. Lett., 33, L15817, doi:10.1029/2006GL026660, 2006.; Berndt, T., Böge, O., and Stratmann, F.: Conference Abstract: Atmospheric H2SO4/H2O Particle Formation: Mechanistic Investigations. 17th International Conference on Nucleation and Atmospheric Aerosols (ICNAA), Galway, Ireland, 69–72, 2007.; Berndt, T., Stratmann, F., Bräsel, S., Heintzenberg, J., Laaksonen, A., and Kulmala, M.: SO2 oxidation products other than H2SO4 as a trigger of new particle formation. Part~1: Laboratory investigations, Atmos. Chem. Phys., 8, 6365–6374, 2008.; Burkholder, J. B., Baynar, T., Ravishankara, A. R., and Lovejoy, E. R.: Particle nucleation following the O3 and OH initiated oxidation of α-pinene and β-pinene between 278 and 320 K, J. Geophys. Res. 112, D10216, doi:10.1029/2006JD007783, 2007.; Curtiss, L. A., Raghavachari, K., Trucks, G. W., and Pople, J. A.: Gaussian-2 theory for molecular energies of first- and second-row compounds, J. Chem. Phys., 94, 7221–7230, 1991.; Das, T. N.: Reactivity and Role of SO$_5^-$ Radical in Aqueous Medium Chain Oxidation of Sulfite to Sulfate and Atmospheric Sulfuric Acid Generation, J. Phys. Chem. A., 105, 9142–9155, 2001.


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