{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,6,10]],"date-time":"2026-06-10T15:09:38Z","timestamp":1781104178953,"version":"3.54.1"},"reference-count":59,"publisher":"National Academy of Sciences","issue":"6","license":[{"start":{"date-parts":[[2024,1,29]],"date-time":"2024-01-29T00:00:00Z","timestamp":1706486400000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by-nc-nd\/4.0\/"}],"funder":[{"DOI":"10.13039\/100000181","name":"DOD | USAF | AMC | Air Force Office of Scientific Research","doi-asserted-by":"publisher","award":["FA9550-22-1-0350"],"award-info":[{"award-number":["FA9550-22-1-0350"]}],"id":[{"id":"10.13039\/100000181","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/100000015","name":"U.S. Department of Energy","doi-asserted-by":"publisher","award":["DE-SC0018679"],"award-info":[{"award-number":["DE-SC0018679"]}],"id":[{"id":"10.13039\/100000015","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":["www.pnas.org"],"crossmark-restriction":true},"short-container-title":["Proc. Natl. Acad. Sci. U.S.A."],"published-print":{"date-parts":[[2024,2,6]]},"abstract":"<jats:p>\n                    SO\n                    <jats:sub>2<\/jats:sub>\n                    (Sulfur dioxide) is the major precursor to the production of sulfuric acid (H\n                    <jats:sub>2<\/jats:sub>\n                    SO\n                    <jats:sub>4<\/jats:sub>\n                    ), contributing to acid rain and atmospheric aerosols. Sulfuric acid formed from SO\n                    <jats:sub>2<\/jats:sub>\n                    generates light-reflecting sulfate aerosol particles in the atmosphere. This property has prompted recent geoengineering proposals to inject sulfuric acid or its precursors into the Earth\u2019s atmosphere to increase the planetary albedo to counteract global warming. SO\n                    <jats:sub>2<\/jats:sub>\n                    oxidation in the atmosphere by the hydroxyl radical HO to form HOSO\n                    <jats:sub>2<\/jats:sub>\n                    is a key rate-limiting step in the mechanism for forming acid rain. However, the dynamics of the HO + SO\n                    <jats:sub>2<\/jats:sub>\n                    \u2192 HOSO\n                    <jats:sub>2<\/jats:sub>\n                    reaction and its slow rate in the atmosphere are poorly understood to date. Herein, we use photoelectron spectroscopy of cryogenically cooled HOSO\n                    <jats:sub>2<\/jats:sub>\n                    <jats:bold>\n                      <jats:sup>\u2013<\/jats:sup>\n                    <\/jats:bold>\n                    anion to access the neutral HOSO\n                    <jats:sub>2<\/jats:sub>\n                    radical near the transition state of the HO + SO\n                    <jats:sub>2<\/jats:sub>\n                    reaction. Spectroscopic and dynamic calculations are conducted on the first ab initio-based full-dimensional potential energy surface to interpret the photoelectron spectra of HOSO\n                    <jats:sub>2<\/jats:sub>\n                    <jats:bold>\n                      <jats:sup>\u2013<\/jats:sup>\n                    <\/jats:bold>\n                    and to probe the dynamics of the HO + SO\n                    <jats:sub>2<\/jats:sub>\n                    reaction. In addition to the finding of a unique pre-reaction complex (HO\u22efSO\n                    <jats:sub>2<\/jats:sub>\n                    ) directly connected to the transition state, dynamic calculations reveal that the accessible phase space for the HO + SO\n                    <jats:sub>2<\/jats:sub>\n                    \u2192 HOSO\n                    <jats:sub>2<\/jats:sub>\n                    reaction is extremely narrow, forming a key reaction bottleneck and slowing the reaction rate in the atmosphere, despite the low reaction barrier. This study underlines the importance of understanding the full multidimensional potential energy surface to elucidate the dynamics of complex bimolecular reactions involving polyatomic reactants.\n                  <\/jats:p>","DOI":"10.1073\/pnas.2314819121","type":"journal-article","created":{"date-parts":[[2024,1,29]],"date-time":"2024-01-29T15:00:21Z","timestamp":1706540421000},"update-policy":"https:\/\/doi.org\/10.1073\/pnas.cm10313","source":"Crossref","is-referenced-by-count":17,"title":["Probing the dynamics and bottleneck of the key atmospheric SO\n                    <sub>2<\/sub>\n                    oxidation reaction by the hydroxyl radical"],"prefix":"10.1073","volume":"121","author":[{"ORCID":"https:\/\/orcid.org\/0000-0001-8461-6889","authenticated-orcid":false,"given":"Dao-Fu","family":"Yuan","sequence":"first","affiliation":[{"name":"Hefei National Research Center for Physical Science at Microscale, University of Science and Technology of China, Hefei 230026, China"},{"name":"Department of Chemistry, Brown University, Providence, RI 02912"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-5939-0846","authenticated-orcid":false,"given":"Yang","family":"Liu","sequence":"additional","affiliation":[{"name":"School of Chemistry and Chemical Engineering, Chongqing University, Chongqing 401331, China"},{"name":"Department of Chemistry and Chemical Biology, Center for Computational Chemistry, University of New Mexico, Albuquerque, NM 87131"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-6258-7191","authenticated-orcid":false,"given":"Tarek","family":"Trabelsi","sequence":"additional","affiliation":[{"name":"Department of Earth and Environmental Sciences, University of Pennsylvania, Philadelphia, PA 19104"},{"name":"Department of Chemistry, University of Pennsylvania, Philadelphia, PA 19104"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-4405-2967","authenticated-orcid":false,"given":"Yue-Rou","family":"Zhang","sequence":"additional","affiliation":[{"name":"Department of Chemistry, Brown University, Providence, RI 02912"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-2392-8322","authenticated-orcid":false,"given":"Jun","family":"Li","sequence":"additional","affiliation":[{"name":"School of Chemistry and Chemical Engineering, Chongqing University, Chongqing 401331, China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-5461-1486","authenticated-orcid":false,"given":"Joseph S.","family":"Francisco","sequence":"additional","affiliation":[{"name":"Department of Earth and Environmental Sciences, University of Pennsylvania, Philadelphia, PA 19104"},{"name":"Department of Chemistry, University of Pennsylvania, Philadelphia, PA 19104"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-9901-053X","authenticated-orcid":false,"given":"Hua","family":"Guo","sequence":"additional","affiliation":[{"name":"Department of Chemistry and Chemical Biology, Center for Computational Chemistry, University of New Mexico, Albuquerque, NM 87131"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-1816-5738","authenticated-orcid":false,"given":"Lai-Sheng","family":"Wang","sequence":"additional","affiliation":[{"name":"Department of Chemistry, Brown University, Providence, RI 02912"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"341","published-online":{"date-parts":[[2024,1,29]]},"reference":[{"key":"e_1_3_4_1_2","volume-title":"Atmospheric Chemistry: Fundamental and Experimental Techniques","author":"Finlayson-Pitts B. 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