{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,10,15]],"date-time":"2026-10-15T06:49:35Z","timestamp":1792046975965,"version":"4.4.0"},"reference-count":55,"publisher":"Wiley","issue":"13","license":[{"start":{"date-parts":[[2026,7,10]],"date-time":"2026-07-10T00:00:00Z","timestamp":1783641600000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/creativecommons.org\/licenses\/by\/4.0\/"},{"start":{"date-parts":[[2026,7,10]],"date-time":"2026-07-10T00:00:00Z","timestamp":1783641600000},"content-version":"tdm","delay-in-days":0,"URL":"http:\/\/doi.wiley.com\/10.1002\/tdm_license_1.1"}],"content-domain":{"domain":["chemistry-europe.onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["ChemPhysChem"],"published-print":{"date-parts":[[2026,7,14]]},"abstract":"<jats:p>Antioxidants operate in biological environments where solvent effects dramatically alter their redox properties. Using ascorbic acid (vitamin C) as a paradigmatic example, we present a comprehensive quantum chemical investigation of its global chemical reactivity indices\u2014ionization potential, electron affinity, HOMO\u2010LUMO gap, hardness, softness, electronegativity, electrophilicity, and electrodonating\/accepting powers\u2014computed at the compound chemistry CBS\u2010QB3 and various DFT levels in vacuo and across six solvents. The results demonstrate that solvation stabilizes charged species so strongly that reactivity indices shift by several electronvolts, following a roughly Born\u2010like dependence on dielectric constant. Most importantly, we show unequivocally that Koopmans\u2019 theorem, often used to estimate these indices from orbital energies, fails catastrophically in solution: it predicts solvent\u2010independent values that are qualitatively and quantitatively wrong, missing the essential physics of dielectric screening and geometric relaxation. We therefore conclude that Koopmans\u2019 theorem must be abandoned for antioxidant studies in condensed phases; adiabatic calculations with solvent are mandatory for meaningful predictions.<\/jats:p>","DOI":"10.1002\/cphc.70375","type":"journal-article","created":{"date-parts":[[2026,7,11]],"date-time":"2026-07-11T03:37:28Z","timestamp":1783741048000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["The Illusion of Simplicity: The Dramatic Failure of Koopmans\u2019 Theorem for Antioxidants in Solvents\u2014The Ascorbic Acid Paradigm"],"prefix":"10.1002","volume":"27","author":[{"ORCID":"https:\/\/orcid.org\/0000-0003-4860-5757","authenticated-orcid":false,"given":"Ioan","family":"B\u00e2ldea","sequence":"first","affiliation":[{"name":"Theoretical Chemistry Heidelberg University  Heidelberg Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2026,7,10]]},"reference":[{"key":"e_1_2_10_2_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.redox.2017.11.017"},{"key":"e_1_2_10_3_1","doi-asserted-by":"publisher","DOI":"10.1002\/qua.25665"},{"key":"e_1_2_10_4_1","doi-asserted-by":"publisher","DOI":"10.1039\/D5SC05463J"},{"key":"e_1_2_10_5_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.accounts.5c00552"},{"key":"e_1_2_10_6_1","doi-asserted-by":"publisher","DOI":"10.1016\/S0031-8914(34)90011-2"},{"key":"e_1_2_10_7_1","doi-asserted-by":"publisher","DOI":"10.1016\/S0065-3276(08)60541-9"},{"key":"e_1_2_10_8_1","doi-asserted-by":"publisher","DOI":"10.1103\/PhysRevB.18.7165"},{"key":"e_1_2_10_9_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr9904009"},{"key":"e_1_2_10_10_1","doi-asserted-by":"publisher","DOI":"10.1039\/c3nr51290h"},{"key":"e_1_2_10_11_1","volume-title":"Gaussian 16, Revision B.01","author":"Frisch M. 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