Threshold-Dependent Electric Field Responses in CL-20/4,5-MDNI Cocrystals Driven by Stoichiometric Ratio

Threshold-Dependent Electric Field Responses in CL-20/4,5-MDNI Cocrystals Driven by Stoichiometric Ratio | 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 Threshold-Dependent Electric Field Responses in CL-20/4,5-MDNI Cocrystals Driven by Stoichiometric Ratio yuqin Chu, peng Zhang, yang Zhu, peng Ma, Congming Ma This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-9422531/v1 This work is licensed under a CC BY 4.0 License Status: Under Review Version 1 posted 4 You are reading this latest preprint version Abstract Context : to regulate the performance of CL‑20, density functional theory and molecular simulations were used to systematically investigate 1:1 and 1:3 CL‑20/4,5‑MDNI cocrystals under external electric fields. Molecular‑level calculations were performed within −0.010 to +0.010 a.u., and crystal‑level computations within 0 to +0.010 a.u. Results show that external electric fields effectively regulate the N–NO₂ trigger bond length and sensitivity. The 1:1 cocrystal exhibits a monotonic response, while the 1:3 cocrystal shows a non-monotonic threshold response with low sensitivity only in a specific field range. Hydrogen bond analysis indicates that only C–H…O bonds exist in the 1:1 cocrystal, while both C–H…O and C–H…N bonds exist in the 1:3 cocrystal. The electric field polarizes and strengthens the hydrogen bond network, dominating the stability and sensitivity difference.Electrostatic potential and dipole moment analyses reveal monotonic charge separation in the 1:1 cocrystal and a distinct threshold response in the 1:3 cocrystal. The frontier orbital energy gap decreases monotonically with increasing electric field, with the highest stability at zero field.This study clarifies the synergistic mechanism of stoichiometric ratio, hydrogen bond network, and external electric field in CL-20-based cocrystals, supporting the design of high-efficiency and low-sensitivity energetic materials. Methods : density functional theory (DFT) and molecular simulation were adopted. The Dmol 3 module in Materials Studio was used to build 1:1 and 1:3 CL-20/4,5-MDNI cocrystal models, with structural optimization and property calculation performed via PBE functional, GGA method, Grimme's DFT-D dispersion correction and DND basis set (SCF convergence criterion: 1.0 × 10⁻⁵ eV). Gaussian 16 was applied to optimize cocrystal structures with/without external electric field using B3LYP-D3/6-311+G(d,p), and M062X-D3/ma-def2-TZVPP was used for single point energy calculation. Wave function analysis was conducted with Multiwfn and VMD. Molecular-level calculations were performed within the range of −0.010 to +0.010 a.u. with a step size of 0.0025 a.u., while crystal-level computations were carried out within 0 to +0.010 a.u. with a step size of 0.001 a.u. CL-20/4 5-MDNI cocrystal external electric field stoichiometric ratio low-sensitivity energetic material Full Text Additional Declarations No competing interests reported. Cite Share Download PDF Status: Under Review Version 1 posted Editorial decision: Revision requested 20 Apr, 2026 Editor assigned by journal 19 Apr, 2026 Submission checks completed at journal 19 Apr, 2026 First submitted to journal 15 Apr, 2026 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-9422531","acceptedTermsAndConditions":true,"allowDirectSubmit":false,"archivedVersions":[],"articleType":"Research Article","associatedPublications":[],"authors":[{"id":626035388,"identity":"53278988-d4bd-4955-b11e-ef03ed8aa3ed","order_by":0,"name":"yuqin Chu","email":"","orcid":"","institution":"Nanjing Tech University","correspondingAuthor":false,"prefix":"","firstName":"yuqin","middleName":"","lastName":"Chu","suffix":""},{"id":626035390,"identity":"7c0097b0-8a30-4eec-9071-25a6b41eb89d","order_by":1,"name":"peng Zhang","email":"","orcid":"","institution":"Nanjing Tech University","correspondingAuthor":false,"prefix":"","firstName":"peng","middleName":"","lastName":"Zhang","suffix":""},{"id":626035391,"identity":"58659819-0e88-4183-a63e-6b118584a056","order_by":2,"name":"yang Zhu","email":"","orcid":"","institution":"Nanjing Tech University","correspondingAuthor":false,"prefix":"","firstName":"yang","middleName":"","lastName":"Zhu","suffix":""},{"id":626035392,"identity":"42ea0dbb-a904-4231-ab6f-9568727c085a","order_by":3,"name":"peng Ma","email":"data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAAZAAAAAyAQMAAABI0h/eAAAABlBMVEX///8AAABVwtN+AAAACXBIWXMAAA7EAAAOxAGVKw4bAAAA5ElEQVRIiWNgGAWjYPACGwbGBgYGZiALRBMF0hgY20jUcpiBgY1YLbrtZw8+Lvh1Po95fvPBzwUMNrIbDjA/e4BPi9mZvGTjmX23ixnb2JKlZzCkGW84wGZugFfLgRwzad6e24mNbTxmzDwMhxM3HOBhk8Cr5fwb89+8PeeAWvi/AbX8J0LLjRyg4T8OgGxhA2o5QIyWd8nSvA3JQC1pxtI8BkCPHWYzI+Cw3IOfef7YJW5sPvzwM0+FnWzf8eZneLUwMPAwgKPRsAHEAQUVM371EC0MfxgY5AkqHAWjYBSMghELAMmvSYckWPnoAAAAAElFTkSuQmCC","orcid":"","institution":"Nanjing Tech University","correspondingAuthor":true,"prefix":"","firstName":"peng","middleName":"","lastName":"Ma","suffix":""},{"id":626035393,"identity":"f6d970e5-d8d1-4a9b-afcb-e75c87843916","order_by":4,"name":"Congming Ma","email":"","orcid":"","institution":"Nanjing Tech University","correspondingAuthor":false,"prefix":"","firstName":"Congming","middleName":"","lastName":"Ma","suffix":""}],"badges":[],"createdAt":"2026-04-15 06:23:32","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-9422531/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-9422531/v1","draftVersion":[],"editorialEvents":[],"editorialNote":"","failedWorkflow":false,"files":[{"id":108434911,"identity":"933804cb-f0a3-497e-8d34-ba713cef1e9f","added_by":"auto","created_at":"2026-05-04 15:26:26","extension":"pdf","order_by":1,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":1835608,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-9422531/v1_covered_37ed856a-c3fd-4743-b671-fad4e4729d0f.pdf"}],"financialInterests":"No competing interests reported.","formattedTitle":"Threshold-Dependent Electric Field Responses in CL-20/4,5-MDNI Cocrystals Driven by Stoichiometric Ratio","fulltext":[],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":false,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":false,"hideJournal":false,"highlight":"","institution":"","isAcceptedByJournal":false,"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 Hybrid","inReviewEnabled":true,"inReviewRevisionsEnabled":false},"keywords":"CL-20/4,5-MDNI cocrystal, external electric field, stoichiometric ratio, low-sensitivity energetic material","lastPublishedDoi":"10.21203/rs.3.rs-9422531/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-9422531/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003e\u003cstrong\u003eContext\u003c/strong\u003e: to regulate the performance of CL‑20, density functional theory and molecular simulations were used to systematically investigate 1:1 and 1:3 CL‑20/4,5‑MDNI cocrystals under external electric fields. Molecular‑level calculations were performed within −0.010 to +0.010 a.u., and crystal‑level computations within 0 to +0.010 a.u.\u003c/p\u003e\n\u003cp\u003eResults show that external electric fields effectively regulate the N–NO₂ trigger bond length and sensitivity. The 1:1 cocrystal exhibits a monotonic response, while the 1:3 cocrystal shows a non-monotonic threshold response with low sensitivity only in a specific field range. Hydrogen bond analysis indicates that only C–H…O bonds exist in the 1:1 cocrystal, while both C–H…O and C–H…N bonds exist in the 1:3 cocrystal. The electric field polarizes and strengthens the hydrogen bond network, dominating the stability and sensitivity difference.Electrostatic potential and dipole moment analyses reveal monotonic charge separation in the 1:1 cocrystal and a distinct threshold response in the 1:3 cocrystal. The frontier orbital energy gap decreases monotonically with increasing electric field, with the highest stability at zero field.This study clarifies the synergistic mechanism of stoichiometric ratio, hydrogen bond network, and external electric field in CL-20-based cocrystals, supporting the design of high-efficiency and low-sensitivity energetic materials.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eMethods\u003c/strong\u003e: density functional theory (DFT) and molecular simulation were adopted. The Dmol\u003csup\u003e3\u003c/sup\u003e module in Materials Studio was used to build 1:1 and 1:3 CL-20/4,5-MDNI cocrystal models, with structural optimization and property calculation performed via PBE functional, GGA method, Grimme's DFT-D dispersion correction and DND basis set (SCF convergence criterion: 1.0 × 10⁻⁵ eV). 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