Size-Dependent Structural Motifs in PtnV− (n = 2–13) cluster anions: A DFT insight

Size-Dependent Structural Motifs in PtnV− (n = 2–13) cluster anions: A DFT insight | 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 Short Report Size-Dependent Structural Motifs in Pt n V − (n = 2–13) cluster anions: A DFT insight P. L. Rodríguez-Kessler, A. R. Rodríguez-Domínguez, Alvaro Muñoz-Castro This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-8612529/v1 This work is licensed under a CC BY 4.0 License Status: Published Journal Publication published 20 Feb, 2026 Read the published version in Journal of Nanoparticle Research → Version 1 posted 10 You are reading this latest preprint version Abstract Dated: January 15, 2026) We present a density functional theory (DFT) investigation of vanadium-doped platinum cluster anions, PtnV − (n = 3–13), focusing on their size-dependent structural, energetic, and electronic properties. Global optimization using a Basin Hopping approach reveals a transition from pla-nar or quasi-planar low-symmetry structures at small sizes to compact, highly coordinated three-dimensional motifs as the Pt content increases. Energetic descriptors, including binding energies, second-order energy differences, and HOMO–LUMO gaps, identify n = 3, 5, and 10 as particularly stable cluster sizes. These enhanced stabilities arise from distinct bonding regimes, with strong Pt–V interactions dominating at small sizes and increasing Pt–Pt metallic bonding and electronic delocalization stabilizing larger clusters. A highly symmetric C3v pyramidal structure is identified as the global minimum for Pt10V − , highlighting the stabilizing role of symmetry. Bond-length and Hirshfeld charge analyses reveal nearly constant Pt–V distances and significant charge transfer from V to Pt in small clusters, followed by increased delocalization and bulk-like Pt–Pt bonding with size. Density of states calculations further confirm the crossover from molecule-like to metallic electronic behavior. Overall, these results elucidate fundamental structure–property relationships in PtnV − clusters, relevant for the rational design of V-doped platinum nanoalloys. Full Text Additional Declarations No competing interests reported. Cite Share Download PDF Status: Published Journal Publication published 20 Feb, 2026 Read the published version in Journal of Nanoparticle Research → Version 1 posted Editorial decision: Revision requested 31 Jan, 2026 Reviews received at journal 31 Jan, 2026 Reviews received at journal 26 Jan, 2026 Reviewers agreed at journal 22 Jan, 2026 Reviewers agreed at journal 22 Jan, 2026 Reviewers agreed at journal 22 Jan, 2026 Reviewers invited by journal 22 Jan, 2026 Editor assigned by journal 20 Jan, 2026 Submission checks completed at journal 19 Jan, 2026 First submitted to journal 15 Jan, 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. 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-8612529","acceptedTermsAndConditions":true,"allowDirectSubmit":false,"archivedVersions":[],"articleType":"Short Report","associatedPublications":[],"authors":[{"id":578895817,"identity":"fc886a32-1fc1-4e4a-9a13-16eedcb1ac06","order_by":0,"name":"P. L. 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Global optimization using a Basin Hopping approach reveals a transition from pla-nar or quasi-planar low-symmetry structures at small sizes to compact, highly coordinated three-dimensional motifs as the Pt content increases. Energetic descriptors, including binding energies, second-order energy differences, and HOMO–LUMO gaps, identify n = 3, 5, and 10 as particularly stable cluster sizes. These enhanced stabilities arise from distinct bonding regimes, with strong Pt–V interactions dominating at small sizes and increasing Pt–Pt metallic bonding and electronic delocalization stabilizing larger clusters. A highly symmetric C3v pyramidal structure is identified as the global minimum for Pt10V − , highlighting the stabilizing role of symmetry. Bond-length and Hirshfeld charge analyses reveal nearly constant Pt–V distances and significant charge transfer from V to Pt in small clusters, followed by increased delocalization and bulk-like Pt–Pt bonding with size. Density of states calculations further confirm the crossover from molecule-like to metallic electronic behavior. 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