Energetics of the OH radical H-abstraction reactions from simple aldehydes and their geminal diol forms

Energetics of the OH radical H-abstraction reactions from simple aldehydes and their geminal diol forms | Research Square window.SnipcartSettings = { analytics: { enabled: false } }; (function() { var accessVector = localStorage.getItem('access_vector') || ''; window.dataLayer = window.dataLayer || []; if (accessVector) { window.dataLayer.push({ user: { profile: { profileInfo: { snid: accessVector } } } }); } })(); (function(w,d,s,l,i){w[l]=w[l]||[];w[l].push({'gtm.start':new Date().getTime(),event:'gtm.js'});var f=d.getElementsByTagName(s)[0],j=d.createElement(s),dl=l!='dataLayer'?'&l='+l:'';j.async=true;j.src='https://www.googletagmanager.com/gtm.js?id='+i+dl;f.parentNode.insertBefore(j,f);})(window,document,'script','dataLayer','GTM-K279D39R'); Browse Preprints In Review Journals COVID-19 Preprints AJE Video Bytes Research Tools Research Promotion AJE Professional Editing AJE Rubriq About Preprint Platform In Review Editorial Policies Our Team Advisory Board Help Center Sign In Submit a Preprint Cite Share Download PDF Research Article Energetics of the OH radical H-abstraction reactions from simple aldehydes and their geminal diol forms Zoi Salta, Thomas Schaefer, Nicola Tasinato, Martina Kieninger, and 3 more This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-4361246/v1 This work is licensed under a CC BY 4.0 License Status: Under Review Version 1 posted 9 You are reading this latest preprint version Abstract Context: Carbonyl compounds, especially aldehydes, emitted to the atmosphere, may suffer hydration in aerosols or water droplets in clouds. At the same time, they can react with hydroxyl radicals which may add or abstract hydrogen atoms from these species. The interplay between hydration and hydrogen abstraction is studied using density functional and quantum composite theoretical methods, both in the gas phase and in simulated bulk water. The H-abstraction from the aldehydic and geminal diol forms of formaldehyde, acetaldehyde, glycolaldehyde, glyoxal, methylglyoxal and acrolein are studied to determine whether the substituent has any noticeable effect in the preference for the abstraction of one form or another. It is found that abstraction of the H-atom adjacent to the carbonyl group gives a more stable radical than same abstraction from the geminal diol in the case of formaldehyde, acetaldehyde and glycolaldehyde. The presence of a delocalizing group in the C a (a carbonyl group in glyoxal and methylglyoxal, and a vinyl group in acrolein), reverts this trend and now the abstraction of the H-atom from the geminal diol gives more stable radicals. A further study was conducted abstracting hydrogen atoms from the other different positions in the species considered, both in the aldehydic and geminal diol forms. Only in the case of glycolaldehyde, the radical formed by H-abstraction from the –CH 2 OH group is more stable than any of the other radical species. Abstraction of the hydrogen atom in one of the hydroxyl groups in the geminal diol is equivalent to the addition of the • OH radical to the aldehyde. It leads, in some cases, to decomposition into a smaller radical and a neutral molecule. In these cases, some interesting theoretical differences are observed between the results in gas-phase and (simulated) bulk solvent, as well as with respect to the method of calculation chosen. Methods: DFT (M06-2X, B2PLYP, PW6B95), CCSD(T) and composite (CBS-QB3, jun-ChS, SCVECV-f12) methods using Dunning basis sets and extrapolation to the CBS limit were used to study the energetics of closed shell aldehydes in their keto and geminal-diol forms, as well as the radical derived from them by hydrogen abstraction. Both gas-phase and simulated bulk solvent calculations were performed, in the last case using the Polarizable Continuum Model. Glyoxal Methylglyoxal Hydration Hydrogen abstraction Atmospheric chemistry Full Text Additional Declarations No competing interests reported. Supplementary Files SupplementaryInformation.pdf Cite Share Download PDF Status: Under Review Version 1 posted Editorial decision: Revision requested 06 Jun, 2024 Reviews received at journal 05 Jun, 2024 Reviews received at journal 04 Jun, 2024 Reviewers agreed at journal 24 May, 2024 Reviewers agreed at journal 23 May, 2024 Reviewers invited by journal 14 May, 2024 Editor assigned by journal 06 May, 2024 Submission checks completed at journal 06 May, 2024 First submitted to journal 02 May, 2024 You are reading this latest preprint version Research Square lets you share your work early, gain feedback from the community, and start making changes to your manuscript prior to peer review in a journal. As a division of Research Square Company, we’re committed to making research communication faster, fairer, and more useful. We do this by developing innovative software and high quality services for the global research community. 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Also discoverable on Platform About Our Team In Review Editorial Policies Advisory Board Help Center Resources Author Services Accessibility API Access RSS feed Manage Cookie Preferences © Research Square 2026 | ISSN 2693-5015 (online) Privacy Policy Terms of Service Do Not Sell My Personal Information {"props":{"pageProps":{"initialData":{"identity":"rs-4361246","acceptedTermsAndConditions":true,"allowDirectSubmit":false,"archivedVersions":[],"articleType":"Research Article","associatedPublications":[],"authors":[{"id":299069741,"identity":"f201eb38-c4c8-45a3-b9b0-8f94d29caa7c","order_by":0,"name":"Zoi Salta","email":"","orcid":"","institution":"Scuola Normale Superiore","correspondingAuthor":false,"prefix":"","firstName":"Zoi","middleName":"","lastName":"Salta","suffix":""},{"id":299069742,"identity":"1f8cead0-4f80-42c2-bdcc-e8ac509a8594","order_by":1,"name":"Thomas Schaefer","email":"","orcid":"","institution":"Leibniz Institute for Tropospheric Research (TROPOS)","correspondingAuthor":false,"prefix":"","firstName":"Thomas","middleName":"","lastName":"Schaefer","suffix":""},{"id":299069743,"identity":"d98d901d-2c47-4492-8a60-6054f2f8525b","order_by":2,"name":"Nicola Tasinato","email":"","orcid":"","institution":"Scuola Normale Superiore","correspondingAuthor":false,"prefix":"","firstName":"Nicola","middleName":"","lastName":"Tasinato","suffix":""},{"id":299069744,"identity":"c8b788d5-6bf7-4aef-89f1-9a0f37f1e2ac","order_by":3,"name":"Martina Kieninger","email":"","orcid":"","institution":"Universidad de la República","correspondingAuthor":false,"prefix":"","firstName":"Martina","middleName":"","lastName":"Kieninger","suffix":""},{"id":299069745,"identity":"0b596364-d3c8-40dd-bbeb-51c8daa3860b","order_by":4,"name":"Aline Katz","email":"","orcid":"","institution":"Universidad de la República","correspondingAuthor":false,"prefix":"","firstName":"Aline","middleName":"","lastName":"Katz","suffix":""},{"id":299069746,"identity":"fda954f4-1bd5-444f-aa1d-77cbf5b7c6c2","order_by":5,"name":"Hartmut Herrmann","email":"","orcid":"","institution":"Leibniz Institute for Tropospheric Research (TROPOS)","correspondingAuthor":false,"prefix":"","firstName":"Hartmut","middleName":"","lastName":"Herrmann","suffix":""},{"id":299069747,"identity":"d9998cd4-8500-4978-82e5-2c7535fe0e13","order_by":6,"name":"Oscar N. 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At the same time, they can react with hydroxyl radicals which may add or abstract hydrogen atoms from these species. The interplay between hydration and hydrogen abstraction is studied using density functional and quantum composite theoretical methods, both in the gas phase and in simulated bulk water. The H-abstraction from the aldehydic and geminal diol forms of formaldehyde, acetaldehyde, glycolaldehyde, glyoxal, methylglyoxal and acrolein are studied to determine whether the substituent has any noticeable effect in the preference for the abstraction of one form or another. It is found that abstraction of the H-atom adjacent to the carbonyl group gives a more stable radical than same abstraction from the geminal diol in the case of formaldehyde, acetaldehyde and glycolaldehyde. 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