Thermodynamics and structure of 2D aliphatic alcohol monolayers on graphene within quantum chemical approach

Thermodynamics and structure of 2D aliphatic alcohol monolayers on graphene within quantum chemical approach | 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 Thermodynamics and structure of 2D aliphatic alcohol monolayers on graphene within quantum chemical approach E. S. Kartashynska This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-5737769/v1 This work is licensed under a CC BY 4.0 License Status: Published Journal Publication published 26 Mar, 2025 Read the published version in Theoretical Chemistry Accounts → Version 1 posted 9 You are reading this latest preprint version Abstract The study reports results from the quantum chemical assessment of the spontaneous monolayer formation of fatty alcohols C n H 2n+1 ОН ( n = 6 − 14) at the graphene-like surface modeled by polyaromatic hydrocarbon (PAH) within the PM6-DH2 method. Unlike monolayers of alkanes, lamellae of alcohols on graphene form a herringbone pattern due to the presence of hydrogen O∙∙∙H–O bonds between the hydroxyl groups of two interacting surfactant molecules belonging to neighboring lamellae. Calculations of the thermodynamic parameters of binding for alcohol monomers and dimers with tricircumcoronene have shown that the intermolecular interactions of the terminal fragments of surfactants make a destabilizing contribution to the Gibbs energy of the alcohol association during the formation of a monolayer on a graphene surface. However, C–H∙∙∙π interactions between CH 2 fragments of the alcohol chain and condensed PAH rings are stabilizing, contributing − 4.77 kJ/mol. Their significant advantage is partially countervailed by the formation of energetically unfavorable CH∙∙∙HC interactions of the “e” type between the hydrocarbon chains of interacting alcohol molecules. It results in existence of a threshold length of the alcohol chain, starting from which these compounds are capable of crystalline monolayer formation on graphene-like surfaces. Spontaneous film formation of n -alcohols on graphene at 298 K is possible for surfactants possessing no less that10 carbon atoms in the chain. An increase in the chain length of alcohols by one methylene fragment is equivalent to an increase in the temperature of the film formation in the range from 6 to 22 ° C for alcohols from pentanol to octadecanol, following experimental data. surfactant monolayer graphene thermodynamics PM6-DH2 method non-covalent interactions Full Text Additional Declarations No competing interests reported. Supplementary Files SupplementaryInformation.docx Cite Share Download PDF Status: Published Journal Publication published 26 Mar, 2025 Read the published version in Theoretical Chemistry Accounts → Version 1 posted Editorial decision: Revision requested 30 Jan, 2025 Reviews received at journal 30 Jan, 2025 Reviews received at journal 22 Jan, 2025 Reviewers agreed at journal 10 Jan, 2025 Reviewers agreed at journal 08 Jan, 2025 Reviewers invited by journal 03 Jan, 2025 Editor assigned by journal 31 Dec, 2024 Submission checks completed at journal 31 Dec, 2024 First submitted to journal 30 Dec, 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. 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-5737769","acceptedTermsAndConditions":true,"allowDirectSubmit":false,"archivedVersions":[],"articleType":"Research Article","associatedPublications":[],"authors":[{"id":396232984,"identity":"bfbf0073-cc30-498f-b977-b483599a2af2","order_by":0,"name":"E. S. 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Unlike monolayers of alkanes, lamellae of alcohols on graphene form a herringbone pattern due to the presence of hydrogen O∙∙∙H\u0026ndash;O bonds between the hydroxyl groups of two interacting surfactant molecules belonging to neighboring lamellae.\u003c/p\u003e \u003cp\u003eCalculations of the thermodynamic parameters of binding for alcohol monomers and dimers with tricircumcoronene have shown that the intermolecular interactions of the terminal fragments of surfactants make a destabilizing contribution to the Gibbs energy of the alcohol association during the formation of a monolayer on a graphene surface. However, C\u0026ndash;H∙∙∙π interactions between CH\u003csub\u003e2\u003c/sub\u003e fragments of the alcohol chain and condensed PAH rings are stabilizing, contributing \u0026minus;\u0026thinsp;4.77 kJ/mol. Their significant advantage is partially countervailed by the formation of energetically unfavorable CH∙∙∙HC interactions of the \u0026ldquo;e\u0026rdquo; type between the hydrocarbon chains of interacting alcohol molecules. It results in existence of a threshold length of the alcohol chain, starting from which these compounds are capable of crystalline monolayer formation on graphene-like surfaces.\u003c/p\u003e \u003cp\u003eSpontaneous film formation of \u003cem\u003en\u003c/em\u003e-alcohols on graphene at 298 K is possible for surfactants possessing no less that10 carbon atoms in the chain. An increase in the chain length of alcohols by one methylene fragment is equivalent to an increase in the temperature of the film formation in the range from 6 to 22 \u0026deg; C for alcohols from pentanol to octadecanol, following experimental data.\u003c/p\u003e","manuscriptTitle":"Thermodynamics and structure of 2D aliphatic alcohol monolayers on graphene within quantum chemical approach","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2025-01-02 14:59:01","doi":"10.21203/rs.3.rs-5737769/v1","editorialEvents":[{"type":"communityComments","content":0},{"type":"decision","content":"Revision requested","date":"2025-01-30T21:04:08+00:00","index":"","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2025-01-30T12:51:48+00:00","index":"hide","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2025-01-22T10:10:30+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"158864293175924108549371075966611153672","date":"2025-01-10T06:08:52+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"107480694569614933515285893709175341894","date":"2025-01-08T10:12:22+00:00","index":"hide","fulltext":""},{"type":"reviewersInvited","content":"","date":"2025-01-03T21:26:17+00:00","index":"","fulltext":""},{"type":"editorAssigned","content":"","date":"2024-12-31T15:11:31+00:00","index":"","fulltext":""},{"type":"checksComplete","content":"","date":"2024-12-31T15:09:49+00:00","index":"","fulltext":""},{"type":"submitted","content":"Theoretical Chemistry Accounts","date":"2024-12-30T20:24:14+00:00","index":"","fulltext":""}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"theoretical-chemistry-accounts","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"tcac","sideBox":"Learn more about [Theoretical Chemistry Accounts](http://link.springer.com/journal/214)","snPcode":"214","submissionUrl":"https://submission.nature.com/new-submission/214/3","title":"Theoretical Chemistry Accounts","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"em","reportingPortfolio":"Springer Hybrid","inReviewEnabled":true,"inReviewRevisionsEnabled":false}}],"origin":"","ownerIdentity":"d0ba436f-12aa-40f5-89a2-abf8ca0c1ba6","owner":[],"postedDate":"January 2nd, 2025","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"published-in-journal","subjectAreas":[],"tags":[],"updatedAt":"2025-03-31T16:09:38+00:00","versionOfRecord":{"articleIdentity":"rs-5737769","link":"https://doi.org/10.1007/s00214-025-03181-w","journal":{"identity":"theoretical-chemistry-accounts","isVorOnly":false,"title":"Theoretical Chemistry Accounts"},"publishedOn":"2025-03-26 15:57:11","publishedOnDateReadable":"March 26th, 2025"},"versionCreatedAt":"2025-01-02 14:59:01","video":"","vorDoi":"10.1007/s00214-025-03181-w","vorDoiUrl":"https://doi.org/10.1007/s00214-025-03181-w","workflowStages":[]},"version":"v1","identity":"rs-5737769","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-5737769","identity":"rs-5737769","version":["v1"]},"buildId":"8U1c8b4HqxoKbykW_rLl7","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}