{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,10,17]],"date-time":"2026-10-17T01:41:07Z","timestamp":1792201267501,"version":"4.4.0"},"reference-count":48,"publisher":"National Academy of Sciences","issue":"48","license":[{"start":{"date-parts":[[2023,11,21]],"date-time":"2023-11-21T00:00:00Z","timestamp":1700524800000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by-nc-nd\/4.0\/"}],"funder":[{"DOI":"10.13039\/100006151","name":"DOE | SC | Basic Energy Sciences","doi-asserted-by":"publisher","award":["DE-SC0018164"],"award-info":[{"award-number":["DE-SC0018164"]}],"id":[{"id":"10.13039\/100006151","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/100006151","name":"DOE | SC | Basic Energy Sciences","doi-asserted-by":"publisher","award":["DE-AC02-06CH11357"],"award-info":[{"award-number":["DE-AC02-06CH11357"]}],"id":[{"id":"10.13039\/100006151","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":[[2023,11,28]]},"abstract":"<jats:p>\n                    Atmospheric formic acid is severely underpredicted by models. A recent study proposed that this discrepancy can be resolved by abundant formic acid production from the reaction (\n                    <jats:xref ref-type=\"disp-formula\">1<\/jats:xref>\n                    ) between hydroxyl radical and methanediol derived from in-cloud formaldehyde processing and provided a chamber-experiment-derived rate constant,\n                    <jats:italic>k<\/jats:italic>\n                    <jats:sub>1<\/jats:sub>\n                    = 7.5 \u00d7 10\n                    <jats:sup>\u221212<\/jats:sup>\n                    cm\n                    <jats:sup>3<\/jats:sup>\n                    s\n                    <jats:sup>\u22121<\/jats:sup>\n                    . High-level accuracy coupled cluster calculations in combination with\n                    <jats:italic>E,J<\/jats:italic>\n                    -resolved two-dimensional master equation analyses yield\n                    <jats:italic>k<\/jats:italic>\n                    <jats:sub>1<\/jats:sub>\n                    = (2.4 \u00b1 0.5) \u00d7 10\n                    <jats:sup>\u221212<\/jats:sup>\n                    cm\n                    <jats:sup>3<\/jats:sup>\n                    s\n                    <jats:sup>\u22121<\/jats:sup>\n                    for relevant atmospheric conditions (\n                    <jats:italic>T<\/jats:italic>\n                    = 260\u2013310 K and\n                    <jats:italic>P<\/jats:italic>\n                    = 0\u20131 atm). We attribute this significant discrepancy to HCOOH formation from other molecules in the chamber experiments. More importantly, we show that reversible aqueous processes result indirectly in the equilibration on a 10 min. time scale of the gas-phase reaction\n                    <jats:inline-formula>\n                      <mml:math xmlns:mml=\"http:\/\/www.w3.org\/1998\/Math\/MathML\" display=\"inline\" overflow=\"scroll\">\n                        <mml:mi>HCHO<\/mml:mi>\n                        <mml:mo>+<\/mml:mo>\n                        <mml:msub>\n                          <mml:mi mathvariant=\"normal\">H<\/mml:mi>\n                          <mml:mn>2<\/mml:mn>\n                        <\/mml:msub>\n                        <mml:mi mathvariant=\"normal\">O<\/mml:mi>\n                        <mml:mo stretchy=\"false\">\u21cc<\/mml:mo>\n                        <mml:msub>\n                          <mml:mi>HOCH<\/mml:mi>\n                          <mml:mn>2<\/mml:mn>\n                        <\/mml:msub>\n                        <mml:mi>OH<\/mml:mi>\n                      <\/mml:math>\n                    <\/jats:inline-formula>\n                    (2) with a HOCH\n                    <jats:sub>2<\/jats:sub>\n                    OH to HCHO ratio of only\n                    <jats:italic>ca<\/jats:italic>\n                    . 2%. Although HOCH\n                    <jats:sub>2<\/jats:sub>\n                    OH outgassing upon cloud evaporation typically increases this ratio by a factor of 1.5\u20135, as determined by numerical simulations, its in-cloud reprocessing is shown using a global model to strongly limit the gas-phase sink and the resulting production of formic acid. Based on the combined findings in this work, we derive a range of 1.2\u20138.5 Tg\/y for the global HCOOH production from cloud-derived HOCH\n                    <jats:sub>2<\/jats:sub>\n                    OH reacting with OH. The best estimate, 3.3 Tg\/y, is about 30 times less than recently reported. The theoretical equilibrium constant\n                    <jats:italic>K<\/jats:italic>\n                    <jats:sub>eq<\/jats:sub>\n                    (2) determined in this work also allows us to estimate the Henry\u2019s law constant of methanediol (8.1 \u00d7 10\n                    <jats:sup>5<\/jats:sup>\n                    M atm\n                    <jats:sup>\u22121<\/jats:sup>\n                    at 280 K).\n                  <\/jats:p>","DOI":"10.1073\/pnas.2304650120","type":"journal-article","created":{"date-parts":[[2023,11,21]],"date-time":"2023-11-21T13:55:59Z","timestamp":1700574959000},"update-policy":"https:\/\/doi.org\/10.1073\/pnas.cm10313","source":"Crossref","is-referenced-by-count":14,"title":["Methanediol from cloud-processed formaldehyde is only a minor source of atmospheric formic acid"],"prefix":"10.1073","volume":"120","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-7794-9439","authenticated-orcid":false,"given":"Thanh Lam","family":"Nguyen","sequence":"first","affiliation":[{"name":"Quantum Theory Project, Department of Chemistry, University of Florida, Gainesville, FL 32611"},{"name":"Quantum Theory Project, Department of Physics, University of Florida, Gainesville, FL 32611"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-7434-6317","authenticated-orcid":false,"given":"Jozef","family":"Peeters","sequence":"additional","affiliation":[{"name":"Department of Chemistry, University of Leuven, Leuven B-3001, Belgium"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-5335-2622","authenticated-orcid":false,"given":"Jean-Fran\u00e7ois","family":"M\u00fcller","sequence":"additional","affiliation":[{"name":"Department of Atmospheric Composition, Royal Belgian Institute for Space Aeronomy, Brussels B-1180, Belgium"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Ajith","family":"Perera","sequence":"additional","affiliation":[{"name":"Quantum Theory Project, Department of Chemistry, University of Florida, Gainesville, FL 32611"},{"name":"Quantum Theory Project, Department of Physics, University of Florida, Gainesville, FL 32611"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-8218-0249","authenticated-orcid":false,"given":"David H.","family":"Bross","sequence":"additional","affiliation":[{"name":"Chemical Sciences and Engineering Division, Argonne National Laboratory, Lemont, IL 60439"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-4372-6990","authenticated-orcid":false,"given":"Branko","family":"Ruscic","sequence":"additional","affiliation":[{"name":"Chemical Sciences and Engineering Division, Argonne National Laboratory, Lemont, IL 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