Tetrahedral Frameworks and Helical Chains: oP32– CaC2O5 and mP80– CaCO3 Calcium Carbonates above 100 GPa

Tetrahedral Frameworks and Helical Chains: oP32– CaC2O5 and mP80– CaCO3 Calcium Carbonates above 100 GPa | 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 Tetrahedral Frameworks and Helical Chains: oP32– CaC2O5 and mP80– CaCO3 Calcium Carbonates above 100 GPa Apostolos Pantousas, Georgios Aprilis, Alena Aslandukova, Ilya Kupenko, and 6 more This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-7516922/v1 This work is licensed under a CC BY 4.0 License Status: Under Review Version 1 posted You are reading this latest preprint version Abstract Recent advances in the exploration of carbonates have established their high-pressure crystal chemistry as mainly based on carbon in the sp 3 configuration. Such carbonates, built upon isolated or vertex-sharing \(\:{\text{C}\text{O}}_{4}^{4-}\) tetrahedra, reveal striking structural diversity. Despite extensive research, synthesis of layered or framework carbonates remained a long-standing challenge. Herein we report on the synthesis and full structural characterization of a novel carbonate, oP32 CaC 2 O 5 , obtained at 122 GPa and 2800 K in a laser-heated diamond anvil cell. Crystal structure of oP32 CaC 2 O 5 based on a vertex-sharing tetrahedral framework. In addition, mP80 CaCO 3 was obtained at the same conditions, featuring pyroxene-like chains of vertex-sharing tetrahedra. In contrast to previously reported experimentally observed or theoretically proposed CaCO 3 phases, our single crystal X-ray diffraction data reveal that the structure of mP80 CaCO 3 features both clockwise and counter-clockwise helical chirality of the pyroxene-like chains. Ab initio calculations support experimental findings and indicate thermodynamic stability of oP32 CaC 2 O 5 and mP80 CaCO 3 in the megabar pressure range. Earth and environmental sciences/Planetary science/Geochemistry Physical sciences/Chemistry/Inorganic chemistry/Solid-state chemistry Full Text Additional Declarations There is NO Competing Interest. Supplementary Files Ca2CO5122GPa.cif Crystallographic Information File Ca2CO5 at 122GPa CaCO3122GPa.cif Crystallographic Information File CaCO3 at 122GPa SupportingInformationTetrahedralFrameworksandHelicalChains.docx Supporting Information Document Cite Share Download PDF Status: Under Review 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. 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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-7516922","acceptedTermsAndConditions":true,"allowDirectSubmit":false,"archivedVersions":[],"articleType":"Article","associatedPublications":[],"authors":[{"id":518490986,"identity":"7893538b-41dd-4b53-8ab1-33be7e2927b7","order_by":0,"name":"Apostolos 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CaCO3 Calcium Carbonates above 100 GPa","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-7516922/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-7516922/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eRecent advances in the exploration of carbonates have established their high-pressure crystal chemistry as mainly based on carbon in the \u003cem\u003esp\u003c/em\u003e\u003csup\u003e\u003cem\u003e3\u003c/em\u003e\u003c/sup\u003e configuration. Such carbonates, built upon isolated or vertex-sharing \\(\\:{\\text{C}\\text{O}}_{4}^{4-}\\) tetrahedra, reveal striking structural diversity. Despite extensive research, synthesis of layered or framework carbonates remained a long-standing challenge. Herein we report on the synthesis and full structural characterization of a novel carbonate, oP32 CaC\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e5\u003c/sub\u003e, obtained at 122 GPa and 2800 K in a laser-heated diamond anvil cell. Crystal structure of oP32 CaC\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e5\u003c/sub\u003e based on a vertex-sharing tetrahedral framework. In addition, mP80 CaCO\u003csub\u003e3\u003c/sub\u003e was obtained at the same conditions, featuring pyroxene-like chains of vertex-sharing tetrahedra. In contrast to previously reported experimentally observed or theoretically proposed CaCO\u003csub\u003e3\u003c/sub\u003e phases, our single crystal X-ray diffraction data reveal that the structure of mP80 CaCO\u003csub\u003e3\u003c/sub\u003e features both clockwise and counter-clockwise helical chirality of the pyroxene-like chains. \u003cem\u003eAb initio\u003c/em\u003e calculations support experimental findings and indicate thermodynamic stability of oP32 CaC\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e5\u003c/sub\u003e and mP80 CaCO\u003csub\u003e3\u003c/sub\u003e in the megabar pressure range.\u003c/p\u003e","manuscriptTitle":"Tetrahedral Frameworks and Helical Chains: oP32– CaC2O5 and mP80– CaCO3 Calcium Carbonates above 100 GPa","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2025-10-31 13:17:22","doi":"10.21203/rs.3.rs-7516922/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":"b41413cd-ea63-473b-a223-6f3f1964e0a6","owner":[],"postedDate":"October 31st, 2025","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"under-review","subjectAreas":[{"id":55090746,"name":"Earth and environmental sciences/Planetary science/Geochemistry"},{"id":55090747,"name":"Physical sciences/Chemistry/Inorganic chemistry/Solid-state chemistry"}],"tags":[],"updatedAt":"2025-10-31T13:17:22+00:00","versionOfRecord":[],"versionCreatedAt":"2025-10-31 13:17:22","video":"","vorDoi":"","vorDoiUrl":"","workflowStages":[]},"version":"v1","identity":"rs-7516922","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-7516922","identity":"rs-7516922","version":["v1"]},"buildId":"8U1c8b4HqxoKbykW_rLl7","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}