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The temperature dependence of its g-factor, measured via electron paramagnetic resonance and shifted significantly from the free-electron value, has been suggested to be inconsistent with the conventional picture of an electron localized in a solvent void or \u201ccavity\u201d. Here, we use ab initio molecular dynamics simulations and quantum chemistry calculations to compute the ensemble-averaged, isotropic g-factor for e\u2013(aq) over the entire temperature range of liquid water. A temperature-dependent shift is obtained, in reasonable agreement with experiment, without any qualitative change in either the localized structure of e\u2013(aq) or its average coordination number. Far from being inconsistent with g-factor measurements, persistence of the cavity motif actually supports the rather mild temperature dependence of the g-factor because the amount of spin density hosted in oxygen orbitals is remarkably insensitive to temperature. These results support a cavity-localized picture of e\u2013(aq) from 0\u2013100 \u00b0C at atmospheric pressure. The simulations are also broadly consistent with spectroscopic measurements demonstrating that the molar extinction coefficient is insensitive to temperature and that there are no abrupt temperature-induced changes in the absorption spectrum, even into the supercooled and supercritical water regimes. This analysis further entrenches the cavity-centric picture of e\u2013(aq).<\/jats:p>","DOI":"10.1021\/jacs.6c07020","type":"journal-article","created":{"date-parts":[[2026,9,3]],"date-time":"2026-09-03T16:26:25Z","timestamp":1788452785000},"page":"36675-36686","source":"Crossref","is-referenced-by-count":1,"title":["Temperature Dependence\nof the Hydrated Electron\u2019s\n                    <i>g<\/i>\n                    -Factor\nand Persistence of a Cavity-Localized Electron\nat Elevated Temperature"],"prefix":"10.1021","volume":"148","author":[{"given":"Ar. M.","family":"Fonlon","sequence":"first","affiliation":[{"name":"The Ohio State University , , , ,","place":["Columbus, Ohio, United States, 43210"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-1378-5241","authenticated-orcid":true,"given":"Christopher J.","family":"Mundy","sequence":"additional","affiliation":[{"name":"Pacific Northwest National Laboratory , , , ,","place":["Richland, Washington, United States, 99352"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-1663-2278","authenticated-orcid":true,"given":"John M.","family":"Herbert","sequence":"additional","affiliation":[{"name":"The Ohio State University , , , ,","place":["Columbus, Ohio, United States, 43210"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2026,8,24]]},"reference":[{"key":"2026090312085662200_cit1","doi-asserted-by":"crossref","first-page":"145","DOI":"10.1016\/B978-012509390-3\/50006-0","article-title":"The Solvated Electron","volume-title":"Fundamentals of Radiation Chemistry","author":"Mozumder","year":"1999"},{"key":"2026090312085662200_cit2","first-page":"33","article-title":"The Solvated Electron:\nA Singular Chemical Species","volume-title":"Radiation\nChemistry: From Basics to Applications in Material and Life Sciences","author":"Mostafavi","year":"2008"},{"key":"2026090312085662200_cit3","first-page":"3","article-title":"An Overview\nof the Radiation Chemistry of Liquids","volume-title":"Radiation Chemistry: From Basics to Applications in Material and\nLife Sciences","author":"Buxton","year":"2008"},{"key":"2026090312085662200_cit4","doi-asserted-by":"publisher","first-page":"5578","DOI":"10.1021\/cr300063r","article-title":"Precursors of solvated electrons\nin radiobiological\nphysics and chemistry","volume":"112","author":"Alizadeh","year":"2012","journal-title":"Chem. Rev."},{"key":"2026090312085662200_cit5","doi-asserted-by":"publisher","first-page":"447","DOI":"10.1146\/annurev-physchem-052516-050816","article-title":"The hydrated electron","volume":"68","author":"Herbert","year":"2017","journal-title":"Annu.\nRev. Phys. Chem."},{"key":"2026090312085662200_cit6","doi-asserted-by":"publisher","first-page":"20538","DOI":"10.1039\/C9CP04222A","article-title":"Structure\nof the aqueous electron","volume":"21","author":"Herbert","year":"2019","journal-title":"Phys. Chem. Chem. Phys."},{"key":"2026090312085662200_cit7","doi-asserted-by":"publisher","DOI":"10.1063\/1.3490479","article-title":"A one-electron model\nfor the aqueous electron that\nincludes many-body electron-water polarization: Bulk equilibrium structure,\nvertical electron binding energy, and optical absorption spectrum","volume":"133","author":"Jacobson","year":"2010","journal-title":"J. Chem. Phys."},{"key":"2026090312085662200_cit8","doi-asserted-by":"publisher","first-page":"6171","DOI":"10.1021\/jp802272r","article-title":"Influence of structure\non electron correlation effects\nand electron\u2013water dispersion interactions in anionic water\nclusters","volume":"112","author":"Williams","year":"2008","journal-title":"J. Phys. Chem. A"},{"key":"2026090312085662200_cit9","doi-asserted-by":"publisher","first-page":"1","DOI":"10.1080\/0144235X.2010.535342","article-title":"Nature\u2019s\nmost squishy ion: The important role\nof solvent polarization in the description of the hydrated electron","volume":"30","author":"Herbert","year":"2011","journal-title":"Int. Rev. Phys. Chem."},{"key":"2026090312085662200_cit10","doi-asserted-by":"publisher","first-page":"3071","DOI":"10.1021\/jz301449f","article-title":"Unraveling\nthe complex nature of\nthe hydrated electron","volume":"3","author":"Uhlig","year":"2012","journal-title":"J. Phys. Chem. Lett."},{"key":"2026090312085662200_cit11","doi-asserted-by":"publisher","first-page":"4973","DOI":"10.1021\/acs.jctc.2c00335","article-title":"Understanding the\ntemperature dependence and finite\nsize effects in ab initio MD simulations of the hydrated electron","volume":"18","author":"Park","year":"2022","journal-title":"J. Chem. Theory Comput."},{"key":"2026090312085662200_cit12","doi-asserted-by":"publisher","first-page":"5641","DOI":"10.1021\/cr300144z","article-title":"Theoretical studies of spectroscopy\nand dynamics of\nhydrated electrons","volume":"112","author":"Turi","year":"2012","journal-title":"Chem. Rev."},{"key":"2026090312085662200_cit13","doi-asserted-by":"publisher","first-page":"23","DOI":"10.1021\/ar200062m","article-title":"Structure,\ndynamics, and reactivity of hydrated electrons by ab initio molecular\ndynamics","volume":"45","author":"Marsalek","year":"2012","journal-title":"Acc. Chem. 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Soc."},{"key":"2026090312085662200_cit17","doi-asserted-by":"publisher","first-page":"9148","DOI":"10.1021\/acs.jpca.5b04721","article-title":"A simple ab initio\nmodel for the hydrated electron that matches experiment","volume":"119","author":"Kumar","year":"2015","journal-title":"J. Phys. Chem. A"},{"key":"2026090312085662200_cit18","doi-asserted-by":"publisher","first-page":"2055","DOI":"10.1021\/acs.jpclett.7b00699","article-title":"Electronic\nlevels of excess electrons\nin liquid water","volume":"8","author":"Ambrosio","year":"2017","journal-title":"J. Phys. Chem. Lett."},{"key":"2026090312085662200_cit19","doi-asserted-by":"publisher","first-page":"7442","DOI":"10.1039\/C8SC05101A","article-title":"Picture of\nthe wet electron: A localized\ntransient state in liquid water","volume":"10","author":"Pizzochero","year":"2019","journal-title":"Chem. Sci."},{"key":"2026090312085662200_cit20","doi-asserted-by":"publisher","first-page":"8074","DOI":"10.1021\/acs.jpcb.9b04895","article-title":"Ab initio investigation\nof the resonance Raman spectrum of the hydrated electron","volume":"123","author":"Dasgupta","year":"2019","journal-title":"J. Phys. Chem. B"},{"key":"2026090312085662200_cit21","doi-asserted-by":"publisher","DOI":"10.1063\/1.5089673","article-title":"Analytic energy\ngradients for the\nQM\/MM-Ewald method using atomic charges derived from the electrostatic\npotential: Theory, implementation, and application to ab initio molecular dynamics of the aqueous electron","volume":"150","author":"Holden","year":"2019","journal-title":"J. Chem. Phys."},{"key":"2026090312085662200_cit22","doi-asserted-by":"publisher","DOI":"10.1063\/5.0067861","article-title":"Flexible\nboundary layer using exchange\nfor embedding theories. II. QM\/MM dynamics of the hydrated electron","volume":"155","author":"Shen","year":"2021","journal-title":"J. Chem. Phys."},{"key":"2026090312085662200_cit23","doi-asserted-by":"publisher","first-page":"19668","DOI":"10.1021\/jacs.2c07572","article-title":"Evidence for water\nantibonding orbital mixing in the hydrated electron from its oxygen\n1s x-ray absorption spectrum","volume":"144","author":"Li","year":"2022","journal-title":"J. Am. Chem. Soc."},{"key":"2026090312085662200_cit24","doi-asserted-by":"publisher","first-page":"3890","DOI":"10.1002\/anie.201814053","article-title":"Dynamics of the bulk hydrated electron\nfrom many-body wave-function theory","volume":"58","author":"Wilhelm","year":"2019","journal-title":"Angew.\nChem., Int. Ed."},{"key":"2026090312085662200_cit25","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202209398","article-title":"Temperature dependent properties\nof the aqueous electron","volume":"61","author":"Lan","year":"2022","journal-title":"Angew. Chem., Int.\nEd."},{"key":"2026090312085662200_cit26","doi-asserted-by":"publisher","first-page":"870","DOI":"10.1021\/acs.jpclett.2c03460","article-title":"Birth of\nthe hydrated electron via charge-transfer-to-solvent excitation of\naqueous iodide","volume":"14","author":"Carter-Fenk","year":"2023","journal-title":"J. Phys. Chem. Lett."},{"key":"2026090312085662200_cit27","doi-asserted-by":"publisher","DOI":"10.1038\/s41467-026-70045-7","article-title":"Simulating\nthe photochemical birth\nof the hydrated electron in liquid water","volume":"17","author":"Miro\u0301n","year":"2026","journal-title":"Nat.\nCommun."},{"key":"2026090312085662200_cit28","doi-asserted-by":"publisher","first-page":"2220","DOI":"10.1021\/acs.jpclett.9b00445","article-title":"Partial molar volume of the hydrated\nelectron","volume":"10","author":"Janik","year":"2019","journal-title":"J. Phys. Chem. Lett."},{"key":"2026090312085662200_cit29","doi-asserted-by":"publisher","first-page":"697","DOI":"10.1038\/nchem.1995","article-title":"Direct observation\nof the collapse of the delocalized excess electron in water","volume":"6","author":"Savolainen","year":"2014","journal-title":"Nat. Chem."},{"key":"2026090312085662200_cit30","doi-asserted-by":"publisher","DOI":"10.1038\/s41467-022-34981-4","article-title":"Observation\nof a transient intermediate in the ultrafast relaxation dynamics of\nthe excess electron in strong-field-ionized liquid water","volume":"13","author":"Low","year":"2022","journal-title":"Nat. Commun."},{"key":"2026090312085662200_cit31","doi-asserted-by":"publisher","DOI":"10.1073\/pnas.2216480120","article-title":"The birth and evolution\nof solvated electrons in the water","volume":"120","author":"Novelli","year":"2023","journal-title":"Proc. Natl.\nAcad. Sci. U.S.A."},{"key":"2026090312085662200_cit32","doi-asserted-by":"publisher","first-page":"3262","DOI":"10.1021\/jacs.3c11857","article-title":"Tracking\ncavity formation in electron solvation: Insights from x-ray spectroscopy\nand theory","volume":"146","author":"Sopena Moros","year":"2024","journal-title":"J. Am. Chem. Soc."},{"key":"2026090312085662200_cit33","doi-asserted-by":"publisher","DOI":"10.1038\/s41467-023-44441-2","article-title":"Spectroscopy\nand dynamics of the hydrated electron at the water\/air interface","volume":"15","author":"Jordan","year":"2024","journal-title":"Nat. Commun."},{"key":"2026090312085662200_cit34","unstructured":"Matsuzaki, K.; Kuramochi, H.; Tahara, T.\n          Electron confinement\nwithin a fluctuation \u201cbox\u201d in liquid water, arXiv:2603.12537. arXiv.org e-Print archive, 2026https:\/\/arxiv.org\/abs\/2603.12537."},{"key":"2026090312085662200_cit35","doi-asserted-by":"publisher","first-page":"919","DOI":"10.1038\/201919a0","article-title":"Electron spin\nresonance spectra of\nhydrated electrons prepared by reaction of atomic sodium with ice\nat 77\u00b0 K","volume":"201","author":"Bennett","year":"1964","journal-title":"Nature"},{"key":"2026090312085662200_cit36","doi-asserted-by":"publisher","first-page":"1393","DOI":"10.1039\/J19670001393","article-title":"Trapped electrons\nproduced by the\ndeposition of alkali-metal atoms on ice and solid alcohols at 77\u00b0K.\nPart I. Optical spectra and electron spin resonance spectra","volume":"0","author":"Bennett","year":"1967","journal-title":"J. Chem. Soc. A"},{"key":"2026090312085662200_cit37","doi-asserted-by":"publisher","first-page":"3365","DOI":"10.1063\/1.431826","article-title":"Electron\nspin echo envelope modulation of trapped radicals in disordered glassy\nsystems: Application to the molecular structure around excess electrons\nin \u03b3-irradiated 10 M sodium\nhydroxide alkaline ice glass","volume":"63","author":"Narayana","year":"1975","journal-title":"J. Chem. Phys."},{"key":"2026090312085662200_cit38","doi-asserted-by":"publisher","first-page":"1628","DOI":"10.1021\/j150612a006","article-title":"Electron spin\necho studies of solvation structure","volume":"85","author":"Kevan","year":"1981","journal-title":"J. Phys.\nChem. A"},{"key":"2026090312085662200_cit39","doi-asserted-by":"publisher","first-page":"413","DOI":"10.1016\/0146-5724(81)90043-1","article-title":"Geometrical\nstructure of solvated electrons","volume":"17","author":"Kevan","year":"1981","journal-title":"Radiat. Phys.\nChem."},{"key":"2026090312085662200_cit40","doi-asserted-by":"publisher","first-page":"138","DOI":"10.1021\/ar00065a002","article-title":"Solvated electron\nstructure in glassy matrices","volume":"14","author":"Kevan","year":"1981","journal-title":"Acc. Chem. Res."},{"key":"2026090312085662200_cit41","doi-asserted-by":"publisher","first-page":"3153","DOI":"10.1063\/1.432641","article-title":"ESR line shape\nstudies of trapped\nelectrons in \u03b3-irradiated 17O enriched\n10M NaOH alkaline ice glass: Model for the geometrical\nstructure of the trapped electron","volume":"64","author":"Schlick","year":"1976","journal-title":"J. Chem.\nPhys."},{"key":"2026090312085662200_cit42","doi-asserted-by":"publisher","first-page":"1498","DOI":"10.1021\/j100530a016","article-title":"Second moment studies\nof the electron spin resonance line shape of\ntrapped electrons in sodium-ice condensates. Relation to the molecular\nstructure around trapped electrons","volume":"81","author":"Lin","year":"1977","journal-title":"J. Phys.\nChem. A"},{"key":"2026090312085662200_cit43","doi-asserted-by":"publisher","first-page":"5223","DOI":"10.1021\/jp068278m","article-title":"The structure\nof the hydrated electron. Part 1. Magnetic resonance of internally\ntrapping water anions: A density functional theory study","volume":"111","author":"Shkrob","year":"2007","journal-title":"J. Phys. Chem. A"},{"key":"2026090312085662200_cit44","doi-asserted-by":"publisher","first-page":"221","DOI":"10.1021\/j100596a006","article-title":"Electron paramagnetic resonance and\nelectron\u2013nuclear double resonance line shape studies of trapped\nelectrons in \u03b3-irradiated deuterium-substituted\n10 M sodium hydroxide alkaline ice glass","volume":"78","author":"Bales","year":"1974","journal-title":"J. Phys. Chem. A"},{"key":"2026090312085662200_cit45","doi-asserted-by":"publisher","first-page":"258","DOI":"10.1016\/0009-2614(88)87150-1","article-title":"Hyperfine interactions of deuterium\nnuclei in the nearest surroundings of trapped electrons in alkaline\nglass","volume":"144","author":"Astashkin","year":"1988","journal-title":"Chem. Phys. Lett."},{"key":"2026090312085662200_cit46","doi-asserted-by":"publisher","first-page":"951","DOI":"10.1063\/1.1670165","article-title":"EPR detection\nof the hydrated electron\nin liquid water","volume":"49","author":"Avery","year":"1968","journal-title":"J. Chem. Phys."},{"key":"2026090312085662200_cit47","doi-asserted-by":"publisher","first-page":"1202","DOI":"10.1063\/1.1677345","article-title":"Resolution\nenhanced ESR spectra of\nthe trapped electrons in an alkaline glass","volume":"56","author":"Ohno","year":"1972","journal-title":"J. Chem. Phys."},{"key":"2026090312085662200_cit48","doi-asserted-by":"publisher","first-page":"243","DOI":"10.1021\/ja00417a044","article-title":"Time resolved electron spin resonance spectroscopy.\nIII. Electron spin resonance emission from the hydrated electron.\nPossible evidence for reaction to the triplet state","volume":"98","author":"Fessenden","year":"1976","journal-title":"J. Am. Chem. Soc."},{"key":"2026090312085662200_cit49","doi-asserted-by":"publisher","first-page":"3511","DOI":"10.1021\/j100346a029","article-title":"ESR studies of solvated electron in liquid solution\nusing photolytic production","volume":"93","author":"Jeevarajan","year":"1989","journal-title":"J. Phys. Chem.\nA"},{"key":"2026090312085662200_cit50","doi-asserted-by":"publisher","first-page":"4637","DOI":"10.1063\/1.453776","article-title":"An ESR study\non solvated electrons\nin water and alcohols: Difference in the g factor\nand related analysis of the electronic state by MO calculation","volume":"88","author":"Shiraishi","year":"1988","journal-title":"J. Chem. Phys."},{"key":"2026090312085662200_cit51","doi-asserted-by":"publisher","first-page":"3497","DOI":"10.1021\/j100116a009","article-title":"Medium effects on the ESR spectrum of the hydrated\nelectron","volume":"97","author":"Veselov","year":"1993","journal-title":"J. Phys. Chem. A"},{"key":"2026090312085662200_cit52","doi-asserted-by":"publisher","first-page":"1766","DOI":"10.1021\/jp909789b","article-title":"Solvated\nelectron extinction coefficient and oscillator strength in high temperature\nwater","volume":"114","author":"Hare","year":"2010","journal-title":"J. Phys. Chem. A"},{"key":"2026090312085662200_cit53","doi-asserted-by":"publisher","first-page":"5232","DOI":"10.1021\/jp0682816","article-title":"The structure of\nthe hydrated electron. Part 2. A mixed quantum\/classical molecular\ndynamics embedded cluster density functional theory theory: Single-excitation\nconfiguration interaction study","volume":"111","author":"Shkrob","year":"2007","journal-title":"J. Phys. Chem.\nA"},{"key":"2026090312085662200_cit54","doi-asserted-by":"publisher","DOI":"10.1063\/5.0253369","article-title":"How the choice of exchange-correlation functional affects\nDFT-based simulations of the hydrated electron","volume":"162","author":"Borrelli","year":"2025","journal-title":"J. Chem. Phys."},{"key":"2026090312085662200_cit55","doi-asserted-by":"publisher","DOI":"10.1063\/1.4829642","article-title":"Extreme density-driven delocalization\nerror for a model solvated-electron system","volume":"139","author":"Johnson","year":"2013","journal-title":"J. Chem. Phys."},{"key":"2026090312085662200_cit56","doi-asserted-by":"publisher","first-page":"5473","DOI":"10.1021\/acs.jctc.6c00234","article-title":"Assessing\nthe limitations of self-interaction-corrected\nfunctionals for describing the hydrated electron","volume":"22","author":"Narvaez","year":"2026","journal-title":"J. Chem. Theory Comput."},{"key":"2026090312085662200_cit57","doi-asserted-by":"publisher","DOI":"10.1063\/1.4905333","article-title":"Isobaric first-principles\nmolecular\ndynamics of liquid water with nonlocal van der Waals interactions","volume":"142","author":"Miceli","year":"2015","journal-title":"J. Chem. Phys."},{"key":"2026090312085662200_cit58","doi-asserted-by":"publisher","DOI":"10.1103\/PhysRevLett.117.186401","article-title":"Ab initio electronic structure of liquid water","volume":"117","author":"Chen","year":"2016","journal-title":"Phys. Rev. Lett."},{"key":"2026090312085662200_cit59","doi-asserted-by":"publisher","first-page":"7456","DOI":"10.1021\/acs.jpcb.6b03876","article-title":"Structural,\ndynamical, and electronic\nproperties of liquid water: A hybrid functional study","volume":"120","author":"Ambrosio","year":"2016","journal-title":"J. Phys. Chem. B"},{"key":"2026090312085662200_cit60","doi-asserted-by":"publisher","first-page":"30281","DOI":"10.1039\/C8CP03682A","article-title":"Reactivity and energy level of a\nlocalized hole in\nliquid water","volume":"20","author":"Ambrosio","year":"2018","journal-title":"Phys. Chem. Chem. Phys."},{"key":"2026090312085662200_cit61","doi-asserted-by":"publisher","DOI":"10.1038\/s41467-024-46772-0","article-title":"Dynamics of\nthe charge transfer to\nsolvent process in aqueous iodide","volume":"15","author":"Lan","year":"2024","journal-title":"Nat. Commun."},{"key":"2026090312085662200_cit62","doi-asserted-by":"publisher","first-page":"23079","DOI":"10.1039\/D5CP02299A","article-title":"Electronic\nenergy levels of aqueous\nhydroxyl species","volume":"27","author":"Ambrosio","year":"2025","journal-title":"Phys. Chem. Chem. Phys."},{"key":"2026090312085662200_cit63","doi-asserted-by":"publisher","DOI":"10.1103\/PhysRevB.54.1703","article-title":"Separable\ndual-space Gaussian pseudopotentials","volume":"54","author":"Goedecker","year":"1996","journal-title":"Phys.\nRev. B"},{"key":"2026090312085662200_cit64","doi-asserted-by":"publisher","DOI":"10.1103\/PhysRevB.58.3641","article-title":"Relativistic separable dual-space\ngaussian pseudopotentials from H to Rn","volume":"58","author":"Hartwigsen","year":"1998","journal-title":"Phys.\nRev. 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