{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2025,10,12]],"date-time":"2025-10-12T04:27:05Z","timestamp":1760243225052,"version":"build-2065373602"},"reference-count":58,"publisher":"MDPI AG","issue":"12","license":[{"start":{"date-parts":[[2014,12,1]],"date-time":"2014-12-01T00:00:00Z","timestamp":1417392000000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Entropy"],"abstract":"<jats:p>In the present work, the mechanisms, thermochemistry and kinetics of the reaction of SO2 with O3\u2212 have been studied using the CCSD(T)\/6-31G(d) + CF method. It has been shown that there exist two possible pathways A and B of the SO2 + O3\u2212 \u2192 SO3\u2212 + O2 reaction. The two pathways\u2019 A and B barrier heights are 0.61 kcal mol\u22121 and 3.40 kcal mol\u22121, respectively, while the energy of the SO2 + O3\u2212 \u2192 SO3\u2212 + O2 reaction is \u221225.25 kcal mol\u22121. The canonical variational transition state theory with small-curvature tunneling (CVT\/SCT) has been applied to study the reaction kinetics. The CVT\/SCT study shows that the rate constants K for pathways A and B, KA = 1.11 \u00d7 10\u221212exp(\u22122526.13\/T) and KB = 2.7 \u00d7 10\u221214exp(\u22121029.25\/T), respectively, grow as the temperature increases and are much larger than those of the  SO2 + O3 \u2192 SO3 + O2 reaction over the entire temperature range of 200\u20131500 K. This indicates that ionization of O3 and high temperatures are favorable for the SO2 oxidation via the reaction with ozone. The new data obtained in the present study can be utilized directly for the evaluation of experiments and model predictions concerning SO2 oxidation and kinetic modeling of gas-phase chemistry of pollutants\/nucleation precursors formed in aircraft engines and the Earth\u2019s atmosphere.<\/jats:p>","DOI":"10.3390\/e16126300","type":"journal-article","created":{"date-parts":[[2014,12,2]],"date-time":"2014-12-02T02:07:08Z","timestamp":1417486028000},"page":"6300-6312","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":4,"title":["Ab intio Investigation of the Thermochemistry and Kinetics of the SO2 + O3\u2212 \u2192 SO3\u2212 + O2 Reaction in Aircraft Engines and the Environment"],"prefix":"10.3390","volume":"16","author":[{"given":"Xuechao","family":"Guo","sequence":"first","affiliation":[{"name":"Environment Research Institute, Shandong University, Jinan 250100, China"},{"name":"State Key Laboratory of Environmental Criteria and Risk Assessment, Chinese Research Academy of Environmental Sciences, Beijing 100012, China"}]},{"given":"Alexey","family":"Nadykto","sequence":"additional","affiliation":[{"name":"Atmospheric Science Research Center, State University of New York at Albany, 251 Fuller Road, Albany, NY 12203, USA"},{"name":"Department of Applied Mathematics, Moscow State Technological University \"STANKIN\", Vadkovsky per., 1, Moscow, 127994, Russia"}]},{"given":"Yisheng","family":"Xu","sequence":"additional","affiliation":[{"name":"State Key Laboratory of Environmental Criteria and Risk Assessment, Chinese Research Academy of Environmental Sciences, Beijing 100012, China"}]},{"given":"Qingzhu","family":"Zhang","sequence":"additional","affiliation":[{"name":"Environment Research Institute, Shandong University, Jinan 250100, China"}]},{"given":"Jingtian","family":"Hu","sequence":"additional","affiliation":[{"name":"Environment Research Institute, Shandong University, Jinan 250100, China"}]}],"member":"1968","published-online":{"date-parts":[[2014,12,1]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"1366","DOI":"10.1126\/science.1189732","article-title":"Getting to the critical nucleus of aerosol formation","volume":"328","author":"Zhang","year":"2010","journal-title":"Science"},{"key":"ref_2","doi-asserted-by":"crossref","first-page":"359","DOI":"10.1038\/nature12663","article-title":"Molecular understanding of sulphuric acid-amine particle nucleation in the atmosphere","volume":"502","author":"Almeida","year":"2013","journal-title":"Nature"},{"key":"ref_3","doi-asserted-by":"crossref","first-page":"1957","DOI":"10.1021\/cr2001756","article-title":"Nucleation and growth of nanoparticles in the atmosphere","volume":"112","author":"Zhang","year":"2012","journal-title":"Chem. Rev"},{"key":"ref_4","doi-asserted-by":"crossref","first-page":"7691","DOI":"10.5194\/acp-9-7691-2009","article-title":"Simulation of particle size distribution with a global aerosol model: Contribution of nucleation to aerosol and CCN number concentrations","volume":"9","author":"Yu","year":"2009","journal-title":"Atmos. Chem. Phys"},{"key":"ref_5","doi-asserted-by":"crossref","first-page":"1243","DOI":"10.1126\/science.1180315","article-title":"The role of sulfuric acid in atmospheric nucleation","volume":"327","author":"Sipila","year":"2010","journal-title":"Science"},{"key":"ref_6","doi-asserted-by":"crossref","first-page":"799","DOI":"10.1002\/ijc.11708","article-title":"Inhaled particles and lung cancer. Part A: Mechanisms","volume":"109","author":"Knaapen","year":"2004","journal-title":"Int. J. Cancer"},{"key":"ref_7","doi-asserted-by":"crossref","first-page":"223","DOI":"10.1038\/ni0305-223","article-title":"Air pollution and allergy: You are what you breathe","volume":"6","author":"Saxon","year":"2005","journal-title":"Nature Immunol"},{"key":"ref_8","doi-asserted-by":"crossref","first-page":"1487","DOI":"10.1126\/science.1095139","article-title":"Atmospheric new particle formation enhanced by organic acids","volume":"304","author":"Zhang","year":"2004","journal-title":"Science"},{"key":"ref_9","doi-asserted-by":"crossref","first-page":"28","DOI":"10.1016\/j.theochem.2010.04.004","article-title":"Formation and properties of hydrogen-bonded complexes of common organic oxalic acid with atmospheric nucleation precursors","volume":"951","author":"Xu","year":"2010","journal-title":"J. Mol. Struct"},{"key":"ref_10","doi-asserted-by":"crossref","unstructured":"Xu, W., and Zhang, R. (2013). A theoretical study of hydrated molecular clusters of amines and dicarboxylic acids. J. Chem. Phys, 139.","DOI":"10.1063\/1.4817497"},{"key":"ref_11","doi-asserted-by":"crossref","first-page":"387","DOI":"10.1021\/jp9068575","article-title":"Interaction between common organic acids and trace nucleation species in the earth\u2019s atmosphere","volume":"114","author":"Xu","year":"2009","journal-title":"J. Phys. Chem. A"},{"key":"ref_12","doi-asserted-by":"crossref","first-page":"4095","DOI":"10.5194\/acp-8-4095-2008","article-title":"Amines are likely to enhance neutral and ion-induced sulfuric acid-water nucleation in the atmosphere more effectively than ammonia","volume":"8","author":"Kurten","year":"2008","journal-title":"Atmos. Chem. Phys"},{"key":"ref_13","doi-asserted-by":"crossref","first-page":"554","DOI":"10.3390\/e13020554","article-title":"Amines in the earth\u2019s atmosphere: A DFT study of the thermochemistry of pre-nucleation clusters","volume":"13","author":"Nadykto","year":"2011","journal-title":"Entropy"},{"key":"ref_14","doi-asserted-by":"crossref","first-page":"42","DOI":"10.1016\/j.cplett.2014.03.036","article-title":"Enhancement in the production of nucleating clusters due to dimethylamine and large uncertainties in the thermochemistry of amine-enhanced nucleation","volume":"609","author":"Nadykto","year":"2014","journal-title":"Chem. Phys. Lett"},{"key":"ref_15","doi-asserted-by":"crossref","first-page":"4797","DOI":"10.1029\/2000JD900539","article-title":"From molecular clusters to nanoparticles: The role of ambient ionization in tropospheric aerosol formation","volume":"106","author":"Yu","year":"2001","journal-title":"J. Geophys. Res"},{"key":"ref_16","doi-asserted-by":"crossref","first-page":"1459","DOI":"10.1029\/1999JD900933","article-title":"Upper tropospheric SO2 conversion into sulfuric acid aerosols and cloud condensation nuclei","volume":"105","author":"Laaksonen","year":"2000","journal-title":"J. Geophys. Res. Atmos"},{"key":"ref_17","doi-asserted-by":"crossref","unstructured":"Liao, H., Zhang, Y., Chen, W.-T., Raes, F., and Seinfeld, J.H. (2009). Effect of chemistry-aerosol-climate coupling on predictions of future climate and future levels of tropospheric ozone and aerosols. J. Geophys. Res, 114.","DOI":"10.1029\/2008JD010984"},{"key":"ref_18","doi-asserted-by":"crossref","first-page":"769","DOI":"10.1098\/rstb.2005.1783","article-title":"Stratospheric ozone depletion","volume":"361","author":"Rowland","year":"2006","journal-title":"Phil. Trans. R. Soc. Lond. B"},{"key":"ref_19","doi-asserted-by":"crossref","first-page":"13","DOI":"10.1016\/j.atmosenv.2008.09.061","article-title":"Air pollution in the last 50 years\u2014From local to global","volume":"43","author":"Fenger","year":"2009","journal-title":"Atmos. Environ"},{"key":"ref_20","doi-asserted-by":"crossref","first-page":"737","DOI":"10.1038\/nature06870","article-title":"Atmospheric oxidation capacity sustained by a tropical forest","volume":"452","author":"Lelieveld","year":"2008","journal-title":"Nature"},{"key":"ref_21","doi-asserted-by":"crossref","first-page":"3603","DOI":"10.1029\/96GL03339","article-title":"Aircraft exhaust sulfur emissions","volume":"23","author":"Brown","year":"1996","journal-title":"Geophys. Res. Lett"},{"key":"ref_22","doi-asserted-by":"crossref","first-page":"399","DOI":"10.1016\/S0360-1285(97)00016-6","article-title":"Investigations on ions in flames","volume":"23","author":"Fialkov","year":"1997","journal-title":"Prog. Energy Combust. Sci"},{"key":"ref_23","doi-asserted-by":"crossref","first-page":"247","DOI":"10.1063\/1.435489","article-title":"Negative ion-molecule reactions of ozone and their implications on the thermochemistry of O3\u2212","volume":"68","author":"Lifshitz","year":"1978","journal-title":"J. Chem. Phys"},{"key":"ref_24","doi-asserted-by":"crossref","first-page":"373","DOI":"10.1016\/0032-0633(67)90201-2","article-title":"Laboratory measurements of negative ion reactions of atmospheric interest","volume":"15","author":"Fehsenfeld","year":"1967","journal-title":"Planet. Space Sci"},{"key":"ref_25","doi-asserted-by":"crossref","first-page":"341","DOI":"10.1016\/0004-6981(83)90050-1","article-title":"Measurements of the oxidation rate of sulfur (IV) by ozone in aqueous solution and their relevance to SO2 conversion in nonurban tropospheric clouds","volume":"17","author":"Maahs","year":"1983","journal-title":"Atmos. Environ. (1967)"},{"key":"ref_26","doi-asserted-by":"crossref","first-page":"1067","DOI":"10.1016\/0004-6981(80)90037-2","article-title":"Kinetic model of atmospheric SO2 oxidation based on published data","volume":"14","year":"1980","journal-title":"Atmos. Environ. (1967)"},{"key":"ref_27","doi-asserted-by":"crossref","first-page":"143","DOI":"10.1021\/jp311103z","article-title":"Reactions and reaction rate of atmospheric SO2 and O3\u2212(H2O)n collisions via molecular dynamics simulations","volume":"117","author":"Bork","year":"2013","journal-title":"J. Phys. Chem. A"},{"key":"ref_28","doi-asserted-by":"crossref","first-page":"3639","DOI":"10.5194\/acp-12-3639-2012","article-title":"Structures and reaction rates of the gaseous oxidation of SO2 by an O3\u2013(H2O)0\u20135 cluster\u2014A density functional theory investigation","volume":"12","author":"Bork","year":"2012","journal-title":"Atmos. Chem. Phys"},{"key":"ref_29","doi-asserted-by":"crossref","first-page":"3695","DOI":"10.5194\/acp-13-3695-2013","article-title":"Exploring the atmospheric chemistry of O2SO3\u2212; and assessing the maximum turnover number of ion-catalysed H2SO4 formation","volume":"13","author":"Bork","year":"2013","journal-title":"Atmos. Chem. Phys"},{"key":"ref_30","doi-asserted-by":"crossref","first-page":"1145","DOI":"10.1016\/0004-6981(86)90147-2","article-title":"On the kinetics and mechanism of oxidation of aquated sulfur dioxide by ozone","volume":"20","author":"Hoffmann","year":"1986","journal-title":"Atmos. Environ. (1967)"},{"key":"ref_31","doi-asserted-by":"crossref","first-page":"591","DOI":"10.1016\/j.fuproc.2005.10.007","article-title":"Removal of sulfur dioxide and nitrogen oxides by using ozone injection and absorption-reduction technique","volume":"87","author":"Mok","year":"2006","journal-title":"Fuel Process. Technol"},{"key":"ref_32","doi-asserted-by":"crossref","first-page":"1775","DOI":"10.1021\/j100611a001","article-title":"Stop-flow time-of-flight mass spectrometry kinetics study. Reaction of ozone with nitrogen dioxide and sulfur dioxide","volume":"78","author":"Davis","year":"1974","journal-title":"J. Phys. Chem"},{"key":"ref_33","first-page":"1","article-title":"Influence of fuel sulfur on the composition of aircraft exhaust plumes: The experiments SULFUR 1\u20137","volume":"107","author":"Schumann","year":"2002","journal-title":"J. Geophys. Res. Atmos. (1984\u20132012)"},{"key":"ref_34","doi-asserted-by":"crossref","first-page":"63","DOI":"10.1016\/S1270-9638(02)01150-1","article-title":"Modeling of sulfur gases and chemiions in aircraft engines","volume":"6","author":"Starik","year":"2002","journal-title":"Aerosp. Sci. Technol"},{"key":"ref_35","doi-asserted-by":"crossref","first-page":"1815","DOI":"10.1139\/v69-296","article-title":"Negative ion-molecule reactions","volume":"47","author":"Ferguson","year":"1969","journal-title":"Can. J. Chem"},{"key":"ref_36","doi-asserted-by":"crossref","first-page":"591","DOI":"10.1016\/j.fuproc.2005.10.007","article-title":"Removal of sulfur dioxide and nitrogen oxides by using ozone injection and absorption-reduction technique","volume":"87","author":"Mok","year":"2006","journal-title":"Fuel Process. Technol"},{"key":"ref_37","doi-asserted-by":"crossref","first-page":"20632","DOI":"10.1021\/ja307523b","article-title":"Sulfuric acid as autocatalyst in the formation of sulfuric acid","volume":"134","author":"Francisco","year":"2012","journal-title":"J. Am. Chem. Soc"},{"key":"ref_38","doi-asserted-by":"crossref","first-page":"10316","DOI":"10.1021\/ja00101a068","article-title":"Ab initio molecular orbital study of the mechanism of the gas phase reaction SO3 + H2O: Importance of the second water molecule","volume":"116","author":"Morokuma","year":"1994","journal-title":"J. Am. Chem. Soc"},{"key":"ref_39","doi-asserted-by":"crossref","first-page":"26","DOI":"10.1016\/j.cplett.2013.07.012","article-title":"Nitric acid catalyzed hydrolysis of SO3 in the formation of sulfuric acid: A theoretical study","volume":"581","author":"Long","year":"2013","journal-title":"Chem. Phys. Lett"},{"key":"ref_40","doi-asserted-by":"crossref","first-page":"2116","DOI":"10.1039\/b916659a","article-title":"The reactions of SO3 with HO2 radical and H2O\u2026HO2 radical complex. Theoretical study on the atmospheric formation of HSO5 and H2SO4","volume":"12","author":"Gonzalez","year":"2010","journal-title":"Phys. Chem. Chem. Phys"},{"key":"ref_41","doi-asserted-by":"crossref","first-page":"17444","DOI":"10.1021\/ja207393v","article-title":"Formic acid catalyzed hydrolysis of SO3 in the gas phase: A barrierless mechanism for sulfuric acid production of potential atmospheric importance","volume":"133","author":"Hazra","year":"2011","journal-title":"J. Am. Chem. Soc"},{"key":"ref_42","first-page":"323","article-title":"Formic acid catalyzed the gas phase reaction of H2O with SO3 and its reverse reaction: A theoretical study","volume":"13","author":"Long","year":"2012","journal-title":"Phys. Chem"},{"key":"ref_43","doi-asserted-by":"crossref","first-page":"1327","DOI":"10.1631\/jzus.A0820787","article-title":"A quantum chemistry study on reaction mechanisms of SO2 with O3 and H2O2","volume":"10","author":"Jiang","year":"2009","journal-title":"J. Zhejiang Univ. Sci. A"},{"key":"ref_44","unstructured":"Frisch, M., Trucks, G., Schlegel, H., Scuseria, G., Robb, M., Cheeseman, J., Montgomery, J., Vreven, T., Kudin, K., and Burant, J. (2004). Gaussian 03, Revision E. 01, Gaussian Inc."},{"key":"ref_45","doi-asserted-by":"crossref","first-page":"5849","DOI":"10.1016\/j.atmosenv.2007.09.023","article-title":"A theoretical investigation of nitrooxyalkyl peroxy radicals from NO3-initiated oxidation of isoprene","volume":"42","author":"Zhao","year":"2008","journal-title":"Atmos. Environ"},{"key":"ref_46","doi-asserted-by":"crossref","first-page":"313","DOI":"10.1016\/j.cplett.2006.08.145","article-title":"Unimolecular ring-cleavage of aromatic bicyclic alkoxy radicals","volume":"432","author":"Suh","year":"2006","journal-title":"Chem. Phys. Lett"},{"key":"ref_47","doi-asserted-by":"crossref","first-page":"1","DOI":"10.1016\/j.cplett.2005.05.122","article-title":"Theoretical study of OH addition to \u03b1- and \u03b2-pinenes","volume":"411","author":"Fan","year":"2005","journal-title":"Chem. Phys. Lett"},{"key":"ref_48","doi-asserted-by":"crossref","first-page":"1","DOI":"10.1063\/1.1862616","article-title":"Ozonolysis mechanisms of \u03b1- and \u03b2-pienes: Kinetics and mechanism","volume":"122","author":"Zhang","year":"2005","journal-title":"J. Chem. Phys"},{"key":"ref_49","doi-asserted-by":"crossref","first-page":"12655","DOI":"10.1021\/ja0350280","article-title":"Oxidation mechanism of aromatic peroxy and bicyclic radicals from OH-toluene reactions","volume":"125","author":"Suh","year":"2003","journal-title":"J. Am. Chem. Soc"},{"key":"ref_50","doi-asserted-by":"crossref","first-page":"9600","DOI":"10.1021\/ja0255195","article-title":"Hydroxyperoxy nitrites and nitrates from OH initiated reactions of isoprene","volume":"124","author":"Zhang","year":"2002","journal-title":"J. Am. Chem. Soc"},{"key":"ref_51","doi-asserted-by":"crossref","first-page":"108","DOI":"10.1016\/j.chemphys.2010.01.003","article-title":"Ab initio investigation of O3 addition to double bonds of limonene","volume":"368","author":"Jiang","year":"2010","journal-title":"Chem. Phys"},{"key":"ref_52","doi-asserted-by":"crossref","first-page":"5354","DOI":"10.1063\/1.1290020","article-title":"Ab initio study of OH addition reaction to isoprene","volume":"113","author":"Lei","year":"2000","journal-title":"J. Chem. Phys"},{"key":"ref_53","doi-asserted-by":"crossref","first-page":"2692","DOI":"10.1021\/ja011518l","article-title":"Mechanism of OH formation from ozonolysis of isoprene: A quantum-chemical study","volume":"124","author":"Zhang","year":"2002","journal-title":"J. Am. Chem. Soc"},{"key":"ref_54","doi-asserted-by":"crossref","first-page":"363","DOI":"10.1021\/ar00072a001","article-title":"The path of chemical reactions\u2014the IRC approach","volume":"14","author":"Fukui","year":"1981","journal-title":"Acc. Chem. Res"},{"key":"ref_55","doi-asserted-by":"crossref","first-page":"4068","DOI":"10.1021\/es802835e","article-title":"Mechanistic and kinetic studies on the homogeneous gas-phase formation of PCDD\/Fs from 2, 4, 5-trichlorophenol","volume":"43","author":"Qu","year":"2009","journal-title":"Environ. Sci. Technol"},{"key":"ref_56","doi-asserted-by":"crossref","first-page":"7301","DOI":"10.1021\/es801599n","article-title":"A quantum mechanical study on the formation of PCDD\/Fs from 2-chlorophenol as precursor","volume":"42","author":"Zhang","year":"2008","journal-title":"Environ. Sci. Technol"},{"key":"ref_57","unstructured":"Corchado, J.C., Chuang, Y.-Y., Fast, P.L., Hu, W., Liu, Y., Lynch, G., Nguyen, K., Jackels, C., Ramos, A.F., and Ellingson, B. (2007). POLYRATE, version 9.7; Computer Program for the Calculation of Chemical Reaction Rates for Polyatomics, University of Minnesota."},{"key":"ref_58","unstructured":"Available online: http:\/\/kinetics.nist.gov\/kinetics\/Detail?id=1997DEM\/SAN1-266:385 (accessed on 17 November 2014)."}],"container-title":["Entropy"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/1099-4300\/16\/12\/6300\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,11]],"date-time":"2025-10-11T21:10:15Z","timestamp":1760217015000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/1099-4300\/16\/12\/6300"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2014,12,1]]},"references-count":58,"journal-issue":{"issue":"12","published-online":{"date-parts":[[2014,12]]}},"alternative-id":["e16126300"],"URL":"https:\/\/doi.org\/10.3390\/e16126300","relation":{},"ISSN":["1099-4300"],"issn-type":[{"type":"electronic","value":"1099-4300"}],"subject":[],"published":{"date-parts":[[2014,12,1]]}}}