Bridging Electron and Nuclear Motions in Chemical Reactions through Electrostatic Forces from Reactive Orbitals

Bridging Electron and Nuclear Motions in Chemical Reactions through Electrostatic Forces from Reactive Orbitals | 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 Bridging Electron and Nuclear Motions in Chemical Reactions through Electrostatic Forces from Reactive Orbitals Takao Tsuneda, Tetsuya Taketsugu This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-5665594/v1 This work is licensed under a CC BY 4.0 License Status: Published Journal Publication published 19 May, 2025 Read the published version in Communications Chemistry → Version 1 posted You are reading this latest preprint version Abstract This study presents a physics-based framework for understanding chemical reactions, highlighting the critical role of the occupied reactive orbital (ORO), the most stabilized occupied orbital during a reaction, in guiding atomic nuclei via electrostatic forces. These forces, termed reactive-orbital-based electrostatic forces (ROEFs), arise from the negative gradient of orbital energy, creating a direct connection between orbital energy variations and nuclear motion. Through the analysis of 48 representative reactions, we identify two predominant types of ROEF behavior: reactions that sustain reaction-direction ROEFs either from the early stages or just before the transition state. These forces carve grooves along the intrinsic reaction coordinates on the potential energy surface (PES), shaping the reaction pathway. This clarifies which types of electron transfer contribute to lowering the reaction barrier. Remarkably, variations in OROs align closely with the curly arrow diagrams widely used in organic chemistry, bridging the intuitive representation of electron transfer with the rigorous PES-based theoretical framework. This integration facilitates a unified discussion of electron transfer and the electrostatic forces driving nuclear motion. By unifying electronic and nuclear motion theories, this study provides a cohesive framework for understanding the driving forces behind chemical transformations, offering profound insights into the electronic basis of reaction mechanisms. Physical sciences/Chemistry/Theoretical chemistry/Reaction mechanisms Physical sciences/Chemistry/Physical chemistry/Electron transfer Physical sciences/Chemistry/Theoretical chemistry/Density functional theory Full Text Additional Declarations There is NO Competing Interest. Supplementary Files supportinginformation.pdf Supporting information Cite Share Download PDF Status: Published Journal Publication published 19 May, 2025 Read the published version in Communications Chemistry → 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-5665594","acceptedTermsAndConditions":true,"allowDirectSubmit":false,"archivedVersions":[],"articleType":"Article","associatedPublications":[],"authors":[{"id":393148254,"identity":"7681fc8f-3100-49b5-aba6-6260e1077d96","order_by":0,"name":"Takao Tsuneda","email":"data:image/png;base64,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","orcid":"https://orcid.org/0000-0002-0249-5276","institution":"Hokkaido University","correspondingAuthor":true,"prefix":"","firstName":"Takao","middleName":"","lastName":"Tsuneda","suffix":""},{"id":393148255,"identity":"5379fa88-385f-46a6-b53a-eab13b297256","order_by":1,"name":"Tetsuya Taketsugu","email":"","orcid":"https://orcid.org/0000-0002-1337-6694","institution":"Hokkaido University","correspondingAuthor":false,"prefix":"","firstName":"Tetsuya","middleName":"","lastName":"Taketsugu","suffix":""}],"badges":[],"createdAt":"2024-12-18 03:20:40","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-5665594/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-5665594/v1","draftVersion":[],"editorialEvents":[{"content":"https://doi.org/10.1038/s42004-025-01556-5","type":"published","date":"2025-05-19T04:00:00+00:00"}],"editorialNote":"","failedWorkflow":false,"files":[{"id":83110391,"identity":"31c24fb7-e422-46b8-946a-2b5231de0164","added_by":"auto","created_at":"2025-05-20 07:09:10","extension":"pdf","order_by":1,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":1494229,"visible":true,"origin":"","legend":"Article File","description":"","filename":"papernat2.pdf","url":"https://assets-eu.researchsquare.com/files/rs-5665594/v1_covered_509ea934-ba12-4b57-854f-ba56eb1de25f.pdf"},{"id":73408943,"identity":"3d4029fa-684a-48cd-8c17-2caf07c3a64d","added_by":"auto","created_at":"2025-01-09 15:49:16","extension":"pdf","order_by":1,"title":"","display":"","copyAsset":false,"role":"supplement","size":1235592,"visible":true,"origin":"","legend":"Supporting information","description":"","filename":"supportinginformation.pdf","url":"https://assets-eu.researchsquare.com/files/rs-5665594/v1/f460146da38c48ae6f49d21c.pdf"}],"financialInterests":"There is \u003cb\u003eNO\u003c/b\u003e Competing Interest.","formattedTitle":"Bridging Electron and Nuclear Motions in Chemical Reactions through Electrostatic Forces from Reactive Orbitals","fulltext":[],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":false,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":false,"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":"nature-portfolio","isNatureJournal":true,"hasQc":false,"allowDirectSubmit":false,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"","title":"Nature Portfolio","twitterHandle":"","acdcEnabled":false,"dfaEnabled":false,"editorialSystem":"ejp","reportingPortfolio":"","inReviewEnabled":true,"inReviewRevisionsEnabled":false},"keywords":"","lastPublishedDoi":"10.21203/rs.3.rs-5665594/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-5665594/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"This study presents a physics-based framework for understanding chemical reactions, highlighting the critical role of the occupied reactive orbital (ORO), the most stabilized occupied orbital during a reaction, in guiding atomic nuclei via electrostatic forces. These forces, termed reactive-orbital-based electrostatic forces (ROEFs), arise from the negative gradient of orbital energy, creating a direct connection between orbital energy variations and nuclear motion. Through the analysis of 48 representative reactions, we identify two predominant types of ROEF behavior: reactions that sustain reaction-direction ROEFs either from the early stages or just before the transition state. These forces carve grooves along the intrinsic reaction coordinates on the potential energy surface (PES), shaping the reaction pathway. This clarifies which types of electron transfer contribute to lowering the reaction barrier. Remarkably, variations in OROs align closely with the curly arrow diagrams\r\nwidely used in organic chemistry, bridging the intuitive representation of electron transfer with the rigorous PES-based theoretical framework. This integration facilitates a unified discussion of electron transfer and the electrostatic forces driving nuclear motion. By unifying electronic and nuclear motion theories, this study provides a cohesive framework for understanding the driving forces behind chemical transformations, offering profound insights into the electronic basis of reaction mechanisms.","manuscriptTitle":"Bridging Electron and Nuclear Motions in Chemical Reactions through Electrostatic Forces from Reactive Orbitals","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2025-01-09 15:49:11","doi":"10.21203/rs.3.rs-5665594/v1","editorialEvents":[],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"communications-chemistry","isNatureJournal":true,"hasQc":false,"allowDirectSubmit":false,"externalIdentity":"commschem","sideBox":"Learn more about [Communications Chemistry](http://www.nature.com/commschem/)","snPcode":"","submissionUrl":"","title":"Communications Chemistry","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"ejp","reportingPortfolio":"Communications Series","inReviewEnabled":true,"inReviewRevisionsEnabled":false}}],"origin":"","ownerIdentity":"74b20530-b681-43ef-ba40-a5dd6a45bfa3","owner":[],"postedDate":"January 9th, 2025","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"published-in-journal","subjectAreas":[{"id":41915006,"name":"Physical sciences/Chemistry/Theoretical chemistry/Reaction mechanisms"},{"id":41915007,"name":"Physical sciences/Chemistry/Physical chemistry/Electron transfer"},{"id":41915008,"name":"Physical sciences/Chemistry/Theoretical chemistry/Density functional theory"}],"tags":[],"updatedAt":"2025-05-20T07:09:04+00:00","versionOfRecord":{"articleIdentity":"rs-5665594","link":"https://doi.org/10.1038/s42004-025-01556-5","journal":{"identity":"communications-chemistry","isVorOnly":false,"title":"Communications Chemistry"},"publishedOn":"2025-05-19 04:00:00","publishedOnDateReadable":"May 19th, 2025"},"versionCreatedAt":"2025-01-09 15:49:11","video":"","vorDoi":"10.1038/s42004-025-01556-5","vorDoiUrl":"https://doi.org/10.1038/s42004-025-01556-5","workflowStages":[]},"version":"v1","identity":"rs-5665594","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-5665594","identity":"rs-5665594","version":["v1"]},"buildId":"8U1c8b4HqxoKbykW_rLl7","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}