Design and Performance Evaluation of Nitrogen-Rich Bis-Six-Membered Fused Ring Energetic Materials via Density Functional Theory

Design and Performance Evaluation of Nitrogen-Rich Bis-Six-Membered Fused Ring Energetic Materials via Density Functional Theory | 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 Design and Performance Evaluation of Nitrogen-Rich Bis-Six-Membered Fused Ring Energetic Materials via Density Functional Theory Qian Zhang, You-Xiang Guo, Tao Long, Lan-Ying Xu, Yan Huang This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-6754812/v1 This work is licensed under a CC BY 4.0 License Status: Published Journal Publication published 01 Aug, 2025 Read the published version in Journal of Molecular Modeling → Version 1 posted 9 You are reading this latest preprint version Abstract Context Density functional theory (DFT) calculations at the M06-2X/def2-TZVP level were employed to design bis-six-membered nitrogen-rich fused ring energetic materials. Six neutral derivatives ( I-2-4 , I-3-4 , I-3-5 , II-2-4 , II-3-4 and II-3-5 ) achieved energy densities exceeding 2.0 g/cm 3 , with energetic salts reaching unprecedented values up to 3.3 g/cm 3 . Non-covalent interaction isosurfaces quantified van der Waals forces in crystal packing, while decomposition pathway simulations for II-3-2 identified a low O-NO 2 BDE (20.24 kcal/mol) coexisting with high thermal stability ( = 765.3 o C), governed by autocatalytic kinetics ( = 24.7 kcal/mol and = 8.44 kcal/mol). The DFT-derived performance matrix ( > 2.02 g/cm 3 , > 600°C, HOFs > 3500 kJ/mol) provides a transferable protocol for balancing energy and safety in molecular modeling of advanced energetics. Method The DFT based geometric optimization and frequency analyses of the designed molecules were determined using M06-2x/def2-TZVP method at Gaussian 09 package suite of programs. The heats of formation (HOF) for all molecules were obtained using an atomization reaction. The kinetic energy (), electrostatic potential (ESP) and other related calculations were computed using Multiwfn_3.8_dev software. The visualization of the weak interaction between dimers was accomplished using VMD 1.9.3 program. Density functional theory Nitrogen-rich fused ring frameworks High-energy-density materials Thermal stability Full Text Additional Declarations No competing interests reported. Supplementary Files JMMsi202504.docx Cite Share Download PDF Status: Published Journal Publication published 01 Aug, 2025 Read the published version in Journal of Molecular Modeling → Version 1 posted Editorial decision: Revision requested 12 Jun, 2025 Reviews received at journal 12 Jun, 2025 Reviews received at journal 07 Jun, 2025 Reviewers agreed at journal 01 Jun, 2025 Reviewers agreed at journal 30 May, 2025 Reviewers invited by journal 30 May, 2025 Editor assigned by journal 28 May, 2025 Submission checks completed at journal 28 May, 2025 First submitted to journal 26 May, 2025 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-6754812","acceptedTermsAndConditions":true,"allowDirectSubmit":false,"archivedVersions":[],"articleType":"Research Article","associatedPublications":[],"authors":[{"id":464204801,"identity":"777c3c25-5708-4d77-b5af-3f1bc8da780e","order_by":0,"name":"Qian Zhang","email":"","orcid":"","institution":"Huanggang Normal University","correspondingAuthor":false,"prefix":"","firstName":"Qian","middleName":"","lastName":"Zhang","suffix":""},{"id":464204802,"identity":"0ef92629-98ae-45da-8ae6-1f0efdf0a880","order_by":1,"name":"You-Xiang Guo","email":"","orcid":"","institution":"Huanggang Normal 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Theory\u003c/p\u003e","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":"journal-of-molecular-modeling","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"jmmo","sideBox":"Learn more about [Journal of Molecular Modeling](https://www.springer.com/journal/894)","snPcode":"894","submissionUrl":"https://submission.nature.com/new-submission/894/3","title":"Journal of Molecular Modeling","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"em","reportingPortfolio":"Springer 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Six neutral derivatives (\u003cb\u003eI-2-4\u003c/b\u003e, \u003cb\u003eI-3-4\u003c/b\u003e, \u003cb\u003eI-3-5\u003c/b\u003e, \u003cb\u003eII-2-4\u003c/b\u003e, \u003cb\u003eII-3-4\u003c/b\u003e and \u003cb\u003eII-3-5\u003c/b\u003e) achieved energy densities exceeding 2.0 g/cm\u003csup\u003e3\u003c/sup\u003e, with energetic salts reaching unprecedented values up to 3.3 g/cm\u003csup\u003e3\u003c/sup\u003e. Non-covalent interaction isosurfaces quantified van der Waals forces in crystal packing, while decomposition pathway simulations for \u003cb\u003eII-3-2\u003c/b\u003e identified a low O-NO\u003csub\u003e2\u003c/sub\u003e BDE (20.24 kcal/mol) coexisting with high thermal stability ( = 765.3 \u003csup\u003eo\u003c/sup\u003eC), governed by autocatalytic kinetics ( = 24.7 kcal/mol and = 8.44 kcal/mol). The DFT-derived performance matrix ( \u0026gt; 2.02 g/cm\u003csup\u003e3\u003c/sup\u003e, \u0026gt; 600\u0026deg;C, HOFs \u0026gt; 3500 kJ/mol) provides a transferable protocol for balancing energy and safety in molecular modeling of advanced energetics.\u003c/p\u003e\u003ch2\u003eMethod\u003c/h2\u003e \u003cp\u003eThe DFT based geometric optimization and frequency analyses of the designed molecules were determined using M06-2x/def2-TZVP method at Gaussian 09 package suite of programs. The heats of formation (HOF) for all molecules were obtained using an atomization reaction. The kinetic energy (), electrostatic potential (ESP) and other related calculations were computed using Multiwfn_3.8_dev software. 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