The mechanism of charge transfer between quantum dots and redox molecules

The mechanism of charge transfer between quantum dots and redox molecules | 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 Article The mechanism of charge transfer between quantum dots and redox molecules Yan Vogel, Willemijn Boeije, Lotte van Steekelenburg, Demi Vollebregt, and 7 more This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-5957346/v1 This work is licensed under a CC BY 4.0 License Status: Published Journal Publication published 14 Jan, 2026 Read the published version in ACS Nano → Version 1 posted You are reading this latest preprint version Abstract Charge transfer between quantum dots (QDs) and redox molecules is not well described by the Marcus theory, the hall-mark theory for charge transfer in molecular systems. The Marcus inverted region, where the rate decreases with increasing the free energy difference, has never been observed in QDs. The previously reported hypothesis for the absence of the Marcus inverted region in QDs is an Auger-assisted charge transfer pathway. Here, we show that the Auger hypothesis does not hold to experimental tests. Instead, our experimental results suggest the presence of a distribution of molecular configurations on the QD surface that results in multiple energy surfaces. We measured the rate constants for two processes where Auger is either allowed or not: charge separation and charge recombination. We used ultrafast transient absorption spectroscopy to probe the rate of charge separation and recombination between PbS QDs and ferrocene derivatives ligands bound to their surface. We find that the rate constant for both charge separation and recombination increase by increasing the free energy difference, are temperature-independent, and increase with the number of molecular acceptors. All these results are against theoretical predictions for an Auger-assisted charge transfer and suggest the presence of multiple molecular configurations with charge transferring through the most favorable pathway. Physical sciences/Nanoscience and technology/Nanoscale materials/Quantum dots Physical sciences/Physics/Chemical physics Full Text Additional Declarations There is NO Competing Interest. Supplementary Files SIVogeletal.pdf Supplementary Information Cite Share Download PDF Status: Published Journal Publication published 14 Jan, 2026 Read the published version in ACS Nano → Version 1 posted 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. Our growing team is made up of researchers and industry professionals working together to solve the most critical problems facing scientific publishing. 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-5957346","acceptedTermsAndConditions":true,"allowDirectSubmit":true,"archivedVersions":[],"articleType":"Article","associatedPublications":[],"authors":[{"id":415439614,"identity":"32895c37-73e1-40c0-b98d-71fb55cb305d","order_by":0,"name":"Yan Vogel","email":"data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAAZAAAAAyAQMAAABI0h/eAAAABlBMVEX///8AAABVwtN+AAAACXBIWXMAAA7EAAAOxAGVKw4bAAAA10lEQVRIie3RMQrCMBSA4UghXV7T9YWCeoQWFwXBq1R6iQ5aO8WlHkDwMCmBuvQAjroL6gXEtC5OJqNg/iWvIR8phBCX6yeD98L8spunoZ4H0opQUN2MvNIflgQzSxLLQHqQr4eU3xq85ogLEkgDYakH7XFCo4zyQ4sIhKUGAvFgL5ql0CQKBBZAILYiG8GVJs/uFgtCHmKVUvQ0KS0IV/rP761MBGST2aHRRBkIO+7qc5oXo9CvL6frao7+tkrO38hY9a+gPra8b+d1o7JfCsMxl8vl+uteahdAmRrKFpUAAAAASUVORK5CYII=","orcid":"https://orcid.org/0000-0003-1975-7292","institution":"Delft University of Technology","correspondingAuthor":true,"prefix":"","firstName":"Yan","middleName":"","lastName":"Vogel","suffix":""},{"id":415439615,"identity":"2c13d282-45a0-425c-bffa-5e2ac143550a","order_by":1,"name":"Willemijn Boeije","email":"","orcid":"","institution":"Delft University of Technology","correspondingAuthor":false,"prefix":"","firstName":"Willemijn","middleName":"","lastName":"Boeije","suffix":""},{"id":415439616,"identity":"efc8a099-888c-4dbe-a547-f22f5062f8be","order_by":2,"name":"Lotte van Steekelenburg","email":"","orcid":"","institution":"Delft University of Technology","correspondingAuthor":false,"prefix":"","firstName":"Lotte","middleName":"van","lastName":"Steekelenburg","suffix":""},{"id":415439617,"identity":"2e5c398e-a49e-4521-9a9d-1a9524966fd6","order_by":3,"name":"Demi Vollebregt","email":"","orcid":"","institution":"Delft University of Technology","correspondingAuthor":false,"prefix":"","firstName":"Demi","middleName":"","lastName":"Vollebregt","suffix":""},{"id":415439618,"identity":"48fe8175-07f1-4676-9254-8294e8c79c1c","order_by":4,"name":"Reinout Ubbink","email":"","orcid":"","institution":"Delft University of Technology","correspondingAuthor":false,"prefix":"","firstName":"Reinout","middleName":"","lastName":"Ubbink","suffix":""},{"id":415439619,"identity":"c64d4457-7e19-4f2d-9ace-f386f9579b42","order_by":5,"name":"Hua Chen","email":"","orcid":"","institution":"Delft University of Technology","correspondingAuthor":false,"prefix":"","firstName":"Hua","middleName":"","lastName":"Chen","suffix":""},{"id":415439620,"identity":"556ae9ff-0fbf-478f-a4fe-c06025a90ac9","order_by":6,"name":"Ali Younesi","email":"","orcid":"","institution":"Max Planck Institute for Polymer Research","correspondingAuthor":false,"prefix":"","firstName":"Ali","middleName":"","lastName":"Younesi","suffix":""},{"id":415439621,"identity":"88121e27-7863-4074-bd35-ffceac4a5937","order_by":7,"name":"Ronald Ulbricht","email":"","orcid":"","institution":"Max Planck Institute for Polymer Research","correspondingAuthor":false,"prefix":"","firstName":"Ronald","middleName":"","lastName":"Ulbricht","suffix":""},{"id":415439622,"identity":"4d128b75-9e79-43b2-9c61-01973a6254bf","order_by":8,"name":"Wolter Jager","email":"","orcid":"","institution":"Delft University of Technology","correspondingAuthor":false,"prefix":"","firstName":"Wolter","middleName":"","lastName":"Jager","suffix":""},{"id":415439623,"identity":"72bc6dc8-14ba-4cfe-819e-1df118ec8edf","order_by":9,"name":"Ferdinand Grozema","email":"","orcid":"https://orcid.org/0000-0002-4375-799X","institution":"Delft University of Technology","correspondingAuthor":false,"prefix":"","firstName":"Ferdinand","middleName":"","lastName":"Grozema","suffix":""},{"id":415439624,"identity":"ce80e297-b409-4b76-b5c7-9ae2583b3018","order_by":10,"name":"Arjan Houtepen","email":"","orcid":"https://orcid.org/0000-0001-8328-443X","institution":"Delft University of Technology","correspondingAuthor":false,"prefix":"","firstName":"Arjan","middleName":"","lastName":"Houtepen","suffix":""}],"badges":[],"createdAt":"2025-02-04 10:40:20","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-5957346/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-5957346/v1","draftVersion":[],"editorialEvents":[{"content":"https://doi.org/10.1021/acsnano.5c13838","type":"published","date":"2026-01-15T00:00:00+00:00"}],"editorialNote":"","failedWorkflow":false,"files":[{"id":100925662,"identity":"44f95bcb-154e-469b-b17e-87e32ca54166","added_by":"auto","created_at":"2026-01-22 22:11:11","extension":"pdf","order_by":1,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":1033818,"visible":true,"origin":"","legend":"Article File","description":"","filename":"MSVogeletal.pdf","url":"https://assets-eu.researchsquare.com/files/rs-5957346/v1_covered_22fca78f-97b1-429a-b7bc-80bdfa07a450.pdf"},{"id":77293834,"identity":"8c9639fe-08c9-4ed0-a9f7-aa85c8da4b3c","added_by":"auto","created_at":"2025-02-27 06:59:25","extension":"pdf","order_by":1,"title":"","display":"","copyAsset":false,"role":"supplement","size":3575365,"visible":true,"origin":"","legend":"Supplementary Information","description":"","filename":"SIVogeletal.pdf","url":"https://assets-eu.researchsquare.com/files/rs-5957346/v1/0161474885b4ba009f0e7ee0.pdf"}],"financialInterests":"There is \u003cb\u003eNO\u003c/b\u003e Competing Interest.","formattedTitle":"The mechanism of charge transfer between quantum dots and redox molecules","fulltext":[],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":false,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":true,"hideJournal":false,"highlight":"","institution":"","isAcceptedByJournal":true,"isAuthorSuppliedPdf":true,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":true,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"researchsquare","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":true,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"/submission","title":"Research Square","twitterHandle":"researchsquare","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"","inReviewEnabled":false,"inReviewRevisionsEnabled":true},"keywords":"","lastPublishedDoi":"10.21203/rs.3.rs-5957346/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-5957346/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"Charge transfer between quantum dots (QDs) and redox molecules is not well described by the Marcus theory, the hall-mark theory for charge transfer in molecular systems. The Marcus inverted region, where the rate decreases with increasing the free energy difference, has never been observed in QDs. The previously reported hypothesis for the absence of the Marcus inverted region in QDs is an Auger-assisted charge transfer pathway. Here, we show that the Auger hypothesis does not hold to experimental tests. Instead, our experimental results suggest the presence of a distribution of molecular configurations on the QD surface that results in multiple energy surfaces. We measured the rate constants for two processes where Auger is either allowed or not: charge separation and charge recombination. We used ultrafast transient absorption spectroscopy to probe the rate of charge separation and recombination between PbS QDs and ferrocene derivatives ligands bound to their surface. We find that the rate constant for both charge separation and recombination increase by increasing the free energy difference, are temperature-independent, and increase with the number of molecular acceptors. All these results are against theoretical predictions for an Auger-assisted charge transfer and suggest the presence of multiple molecular configurations with charge transferring through the most favorable pathway.","manuscriptTitle":"The mechanism of charge transfer between quantum dots and redox molecules","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2025-02-27 06:59:20","doi":"10.21203/rs.3.rs-5957346/v1","editorialEvents":[{"type":"communityComments","content":0}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"researchsquare","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":true,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"/submission","title":"Research Square","twitterHandle":"researchsquare","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"","inReviewEnabled":false,"inReviewRevisionsEnabled":true}}],"origin":"","ownerIdentity":"855bc359-8270-4191-aeb0-b0615135f216","owner":[],"postedDate":"February 27th, 2025","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"published-in-journal","subjectAreas":[{"id":44301485,"name":"Physical sciences/Nanoscience and technology/Nanoscale materials/Quantum dots"},{"id":44301486,"name":"Physical sciences/Physics/Chemical physics"}],"tags":[],"updatedAt":"2026-01-22T22:11:04+00:00","versionOfRecord":{"articleIdentity":"rs-5957346","link":"https://doi.org/10.1021/acsnano.5c13838","journal":{"identity":"acs-nano","isVorOnly":true,"title":"ACS Nano"},"publishedOn":"2026-01-15 00:00:00","publishedOnDateReadable":"January 15th, 2026"},"versionCreatedAt":"2025-02-27 06:59:20","video":"","vorDoi":"10.1021/acsnano.5c13838","vorDoiUrl":"https://doi.org/10.1021/acsnano.5c13838","workflowStages":[]},"version":"v1","identity":"rs-5957346","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-5957346","identity":"rs-5957346","version":["v1"]},"buildId":"8U1c8b4HqxoKbykW_rLl7","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}